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By Fang-Qui Zu

Understanding the nature of liquid structures and properties remains an open problem for many fundamental and applied fields such as materials sciences and processing. And as well known, there is no other defined phase line above liquidus (TL ) in phase diagrams of ordinary binary systems. However, via different experimental resorts, our research results on over 30 metallic melts including alloys and elements show a novel physical image: temperature induced liquid-liquid structure transition (TI-LLST) can occur hundreds of degrees over TL. On the other hand, the solidification behaviors and structures out of the melts experienced TI-LLST are distinct from those out of the melts before TI-LLST. In this presentation, some characteristic aspects of the TI-LLST and the effects on solidification behaviors and structures are briefly summarized, and the pertinent rules and mechanism are also analyzed.

Jan 1, 2009

By Pierre-François Bareel

EU legislation imposes ambitious recycling targets for various consumer goods. End-of-Life Vehicles (ELVs), scrap iron and various proportions of Waste Electrical and Electronic Equipment (WEEE) are processed by shredding plants which recover most of the metals but produce Shredder Residues (SR) which are landfilled. They represent 20 to 25 wt.% of the shredder input. Energy issues for the coarse fraction of SR are now largely studied. However, below 2 mm, the calorific value falls off drastically. These Fine Shredder Residues (FSR) represent up to 55 wt.% of the total SR. To meet European objectives other alternatives to landfilling must be considered for the FSR. The present paper describes a study carried out to characterise the FSR and investigates ways to process them and produce marketable products. Applying Gy's theory, a sampling procedure was conducted over two years to statistically quantify the variability of the physical and chemical properties of FSR produced by a Belgian post-shredding treatment plant. Macroscopic characterisation has led to the identification of four material categories which could be separated according to their physical properties: ferrous metals (more or less oxidised), non-ferrous metals, an organic fraction (plastics, rubber, textiles, foams, wood) and a minerals fraction (glass, ceramic, concrete). The entrainment of small metallic particles within the pores of organic fragments will affect the quality of the separations.

Jan 1, 2006

By Guo Xueyi

The dissolution behaviors of valuable metals, lead and zinc, from secondary fly ash generated in municipal incineration plants were investigated using some lixiviants: sulfuric and hydrochloric acids, acetic acid and some chelating reagents including L-asparaginic-N,N-diacetic acid (ASDA), a biodegradable, and therefore, environmentally benign novel chelating reagent. It was found that zinc exists mainly as ZnO, whereas Pb probably as PbOHCI and PbO, and the easily soluble components in SFA are KCI and NaCl. Suitable amount of HCI can dissolve all of lead and zinc from SFA. Sulfuric acid can selectively extract zinc leaving lead in the residue. Ethylenediaminetetraacetic acid (EDTA) is an effective chelating reagent to extract both zinc and lead. Although ASDA and diethylene¬triaminepentaacetic acid (DTPA) can selectively extract more than half of lead from SFA, it would by no means be regarded as highly effective reagents for the extraction of these metal values. Keywords: Lead, Zinc, Secondary fly ash, Leaching, Dissolution

Jan 1, 2002

By Vitalij K. Pecharsky

Recent interest in complex aluminohydrides as potential near ambient, ultra-high capacity, solid-state sources of hydrogen (e.g., for fuel cells) calls for an improved understanding of the processes occumng in these hydrogen-containing materials during both the release and the uptake of hydrogen. Lithium aluminohydride (LiAlH4) rapidly releases 5.2 wt. % of hydrogen (i.e., nearly four times more than LaNis-based alloys) during mechanochemical processing at ambient conditions in the presence of transition metal catalysts. Using a variety of solid-state characterization techniques, the mechanochemical transformations in a series of LiAlH4 - metal catalyst systems have been examined and preliminary insights on the mechanism have been obtained. Surprisingly, the well-known hydrogenating-dehydrogenating catalysts, such as Ni and Pt, are practically inactive in the mechanochemical dehydrogenation of LiAlH4.

Jan 1, 2002

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 Guillermo Rios, Arbizum Cristina, Joa Viflals, Alba Sunyer

"Atlantic Copper is one of the largest copper producers in Europe. Its production facilities are located in Huelva (Spain) and account for the smelting of over one million tpy of concentrates to produce up to 260 ktpy cathodes and 900 ktpy of sulphuric acid. During copper concentrate smelting, the slag coming from the flash furnace and PS converters are treated in an electrical slag cleaning furnace. As a result of the treatment of the off gases from this furnace, approximately 2,000 tpy of a Zn-rich filter cake are produced and are sent to authorized waste managers. This paper describes the characterization of this material and the preliminary results of a new process to recover zinc as a pure zinc hydroxycarbonate while lead is collected as an indium-rich anglesite product. The behavior of impurities (Cd, As, Tl, Sn, Sb, Bi, Cu, Se, Te) in the leaching, solution purification and precipitation steps is also reported.IntroductionThe Atlantic Copper Metallurgical Complex in Huelva (Spain) was commissioned in 1970 with a capacity of 40,000 tpy of copper from concentrate. In 1975, the old blast furnaces were replaced by Outokumpu flash smelting furnace (FSF) technology, and the copper refinery capacity was increased to 108,000 tpy. Between 1994 and 1996, an expansion project was carried out to increase the copper from concentrate and cathodes to 250,000 tpy and 215,000 tpy, respectively. This expansion basically consisted of a new sulphuric acid plant, replacement of the anode furnaces by two 400 t units, redesign of the slag cleaning furnace (SCF), an increase in the electrolytic cells to 1,120 and implementation of ISA permanent cathode technology. Furthermore, a debottlenecking project has led to a capacity of 1,000,000 tpy of fresh concentrate since 1997. Meanwhile between 1995 and 1998, a cathode production rate of 260,000 tpy was reached as a result of a progressive increase in the current density in the refinery."

Jan 1, 2012

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 Kouji Mimura, Masahito Uchikoshi, Minoru Isshiki

"HfO2 is expected to be a gate dielectric used in ULSI alternatives to S1O2. Although the materials used in ULSI are required to be significantly pure, commercial Hf contains > 2 mass% Zr. It is important to establish a process for removing Zr from Hf. In the present study, anion-exchange separation using a multi-column method was employed. The separation tests were carried out at variety of temperatures and flow rates. The decrease in the flow rate of the mobile phase made the elution curves of both Hf(IV) and Zr(IV) broaden contrary to the case of Co(II), Cu(II), or Fe(III). This is caused by the difference in adsorption rate on the anion exchange resin. In addition, more than one column was connected in series in order to enhance the separation. As a result, the content of Zr(IV) was successfully reduced to 1/100 of that relative to the raw material.IntroductionHafnium is one of the most important materials in modem society. The main applications of Hf metal are as a control rod in a nuclear reactors because of its large neutron-capture cross-section and as an additive to various alloys because of its corrosion resistance [1]. In addition to those applications, attention has been recently paid to HfCh as a high-x"" dielectric used in ultra large scale integration, ULSI, as well as ZrCh, AI2O3 and La2C>3, which are expected to be alternatives to conventional S1O2 thin films [2].The materials used in ULSI are required to have a high purity in order to avoid unexpected errors due to impurities. Furthermore, high purity Hf is indispensable for investigating the intrinsic properties of Hf metal. Thus, it is significant to establish the purification process for Hf from both the industrial and academic perspectives."

Jan 1, 2012

By Joseph Hamuyuni, Pekka Taskinen

We present experimental results for the liquidus in the system Cu2O - CaO -Al2O3 at 1250 oC. In this study, we quantified the liquidus by the equilibration/quench/analysis technique, with Cu2O, Al2O3, and CaO as primary materials exclusively. Experiments were conducted in air at an at oxygen pressure (p) = 21.3 kPa). Equilibrated specimens were quenched in brine solution of 10 wt% NaCl. We then quantified the liquid chemical compositions by means of Energy-Dispersive X-Ray Spectroscopy (EDS) and Electron probe micro-analyzer (EPMA). This study reveals inconsistences in liquidus surface of the present ternary diagram of the system here in mentioned. Differences of up to 10 wt % compositions of the species have been observed.

Jan 1, 2015

By T. Shibaraki

A new larger, more efficient and economical Mitsubishi furnace line at Naoshima was put into operation in May 1991. Naoshima Smelter had produced previously about 230,000 mtpy anode copper with two smelter lines, i.e., a conventional reverberatory furnace line and Mitsubishi furnace line, which had been shutdown at the same time of the start up of the new smelter. At the beginning of the operation, there were several initial problems at the area of off gas trains and feeding system. By overcoming them now the process has been continuing satisfactory operation at the design rate. The paper describes about the design concepts and the actual operation of the new smelter.

Jan 1, 1993

By Luis M. Chia

The direct dissolution of zinc in an organic solution of di-(2-ethylhexyl) phosphoric acid (D2EHPA) and kerosene was studied. The objective was to gain a better understanding of the fundamentals involved in the anodic step of the galvanic stripping process. Results showed that metallic zinc does dissolve spontaneously at ambient temperature by an electrochemical mechanism and the presence of additional oxygen activated the process. When oxygen was removed by prior nitrogen sparging, dissolution did not occur indicating a depolarizing cathodic reaction is necessary. The concentration of water in the organic also affected the rate of dissolution. A factorially designed experiment was made using four variables at two levels selected by evaluating results from previous screening tests. D2EHPA concentration, surface area and agitation were all found to be significant for the values chosen. Temperature was less significant and it was found that zinc dissolution is probably a diffusion or mixed controlled process, as indicated by the calculated activation energy of 6 kcal/mole.

Jan 1, 1995

By Kyle S. Brinkman, Kenneth L. Reifsnider, Fazle Rabbi

"Mixed ionic and electronic conducting (MIEC) ceramic membranes are HeteroFoaM's which play an essential role in a number of energy conversion related systems including the solid oxide fuel cell (SOFC), oxygen separation and permeation membranes, partial oxidization membrane reactors for natural gas processing, and high temperature electrolysis cells. Dual phase oxygen membranes consisting of an ionic conducting phase Ceo.sGdo.z02 (CGO) and an electronic conductive phase C0Fe204 (CFO) were fabricated and characterized by structural (XRD), microstructural (SEM-EDS) and broadband dielectric measurement techniques. In-situ measurements of the dielectric properties of working oxygen separation membranes are presented which indicate that the material's dielectric behavior can be an indicator for MIECperformance.IntroductionCeramic membranes which transport oxygen ions play an essential role in a number of energy conversion related systems including the solid oxide fuel cell (SOFC) [l ], oxygen separation and permeation membranes in the commercial and nuclear arena [2, 3], partial oxidization membrane reactors for natural gas processing [4], and high temperature electrolysis cells [5]. For the electrolyte functions, the membranes must transport oxygen ions only. On the other hand, permeation membranes, typically used in combustion devices to support oxy-fuel combustion or for partial oxidation reactions involving the production of synthesis gases, require mixed oxygen ion and electronic conduction (MIEC). Traditionally the tailoring of the ratio of ionic conductivity to the materials electronic conductivity, measured as the transference number, has been accomplished by the introduction of aliovalent doping elements creating point defects in the material facilitating the diffusion of charged species. However, several decades of research have not yet produced single phase materials which possess the concomitant ionic and electronic conductivity required for use in membrane separation applications. It is clear that novel ""dual phase"" heterogeneous materials will be required and that the surface reactions of these materials will be of particular importance as the industry moves toward thin films membranes [6]."

Jan 1, 2013

By Maija-Leena Metsiirinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high ( up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro- scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEM/EDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to simulate nickel flash smelting process. In the nickel flash furnace, oxidation of concentrate occurs at one end, and reduction of slag occurs at the other. The model makes use two zones, namely the reaction shaft/settler zone and the appendage zone and accounts for 6 phases (matte, slag, silica, magnetite, Cu-Ni alloy and gaseous phase), 13 elements (Ni, Co, Cu, Fe, S, 0, N, C, H, Si, Al, Mg and Ca) and 33 chemical components in nickel flash smelting system. The compositions of matte, slag and gaseous phases in equilibrium are calculated by using the data of free energies of formation and activity coefficients of components. Two nickel sulfide species are used to allow for the modeling of sulfur-deficient mattes. The model predictions are compared with the known industrail data from Kalgoorlie Nickel Smelter, and excellent agreement is obtained. The model can be a very useful tool for monitoring and optimizing the actual industrial operations of nickel smelting process. The distribution behaviors of Ni, Co, Cu, Fe, S and 0 in the nickel smelting furnace depend on the process parameters such as smelting temperature, volumes of air, the content of the elements~ charge and oil.1. IntroductionThe nickel flash smelting furnace essentially consists of a reaction shaft where nickel sulfide concentrate is partially oxidized with air, a settle zone where matte and slag are allowed to separate, and a slag cleaning end where coke is added to provide for the reduction of the oxidized nickel from slag, and electrodes are used to provide heat.The theoretical model to consider a mass balance for copper flash furnace is developed by S. Goto and R. Shimpo[1][2J. However, this can not be true for nickel flash furnace as a whole since oxidation of concentrate occurs at one end (in the reaction shaft/settler), and reduction of slag occurs at the other (in the appendage). Despite these limitations, an acceptable pseudo-thermodynamic description of the furnace can be achieved using essentially two zones, namely the reaction shaft/settler zone and the appendage zone. Compositions of gas, slag and matte in two zones are calculated."

Jan 1, 1998

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

By Jose Bengoa

Low metal prices and environmental restrictions are always a challenge for copper smelters operation and its productivity. Thus, in order to reduce production costs and control gas emissions, improvements of the Teniente Converter (CT) operation were made at 110 Smelter Plant of Southern Peru Copper Co., 110, Peru, and the main objective was to increase its capacity for smelting copper concentrates without affecting normal operation. The present work corresponds to a recent study conducted during the normal industrial operation of the Teniente Converter in this plant and, it shows the effect of increasing air oxygen enrichment from 28 to 34% on its productivity. The results show an increasing of concentrate smelting rate from 800 to 1370 tpd and hence a notorious improving in copper production, and practically no effect on the refractory consumption. The increment of the concentrate throughput, increases also the SO2 concentration and the sulfuric acid production, showing the effort done by this operation in order to accomplish the environmental Peruvian regulation.

Jan 1, 2003

By M. Hashimoto

The equilibrium distribution ratios of sulfur between molten copper and CaO-fluxes containing caF2 and caC12 were determined in the range of 1300° to 1400° C under carbon monoxide. The rate of approach to equilibrium is rapid and increases with increasing CaCll concentration. In CaO-CaFl-CaCl2 fluxes, the distribution ratio varies in a complex way with temperature and CaFl concentration. The results are compared with those obtained with the binary fluxes of CaO with BaFZ and MgFl ?

Jan 1, 1983

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 P. R. Taylor

Laboratory experiments have been performed to evaluate the kinetics of roasting pyrite and arsenopyrite in air at elevated temperatures, in the presence of lime. The effects of temperature, time, air flow rate, particle size, lime type, and mineral/lime weight ratio on the rates of oxidation, lime sulfation, and lime arsenation were studied. The reaction products were identified using chemical analysis, x-ray diffraction, SEM analysis, and optical microscopy. The results are discussed in terms of the utilization of lime to capture sulfur and arsenic during the roasting of refractory precious metal concentrates. More than 99.9% of the arsenic and 98% of the sulfur are contained when roasting pyrite and arsenopyrite with hydrated lime under typical roasting conditions.

Jan 1, 1991

By I. D. Reznik

On blowing nickel matte in a converter without quartz, first the oxidation of metallic iron and a part of FeS occurs without evolving sulfur dioxide, the formed FeO dissolves in a sulphide smelt and form a homogeneous oxysulphide smelt. On further increasing the FeO content, the oxysulphide separates into 2 layers. Based on the laboratory investigation of FeO-(FeS+Fe°) - (Ni3S2+Ni°) ternary phase diagram we have identified the separation region at 1250°C. The boundaries of the separation region have the form of an arc and the composition of the separated oxysulphide layers is defined by the canodes. In the nickel or copper-nickel matte - silicacalcium oxide slag system at 1250°C three layers, namely sulphide, oxysulphide, and slag may be formed. A high slag basicity due to the presence of CaO can serve to enhance the activity of FeO; a low nickel content in the matte corresponds to a high concentration of FeS therein; FeO from slag and FeS from the matte form a homogeneous FeO-FeS solution, i.e. an oxysulphide layer. The investigation on the "Camebaks" apparatus and by the nuclear gamma-ray resonance spectroscopy method of the phase composition in a slowly cooled oxysulphide layer has shown the presence of four phases: wustite, troilite, ferronickel grains, and calcium oxide-silica inclusions. Knowledge of regularities in the oxysulphides formation makes it possible to use them in pyrometallurgy of nickel and cobalt or preventing their formation.

Jan 1, 1997