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By K. Murayama, M. Kawakami, T. Takenaka, S. Yokoyama

"Cokes play an important role of spacer in blast furnace. However, they degenerate during Boudouard reaction. Blast furnace cokes are reacted with pure C02 at I 072 to 1673 K. Reaction rate was obtained by the weight change of spherical specimen. The specimen after reaction was examined by microscopic observation. The reaction rate increased with temperature and was expressed by two Arrhenius type lines. The activation energy was 126 KJ/mol at higher temperature than 13 73 K and 202 KJ/mol at lower temperature range. At the higher temperature range, the reaction proceeded from the surface leaving unreacted core, whereas homogeneously whole inside at lower temperature. The porosity increased from the center to surface at higher temperature, whereas it was almost constant at lower temperature.IntroductionThe cokes have the function of fuel, reductant and spacer to keep gas and liquid flow in the blast furnace. Thus, the reaction mechanism of coke with several gas and the strength after the reaction should be important factor to control the blast furnace operation. The reaction mechanism of coke with C02 has been studied extensively. The rate equations were derived by Gadsby[ I], Ergun[2] and Turkdogan and Vinters[3]. They were compared and discussed by Kobayashi and Omori [ 4]. Effect of crystallization degree on the reaction rate was examined by Kashiwaya and Ishii[5]. Catalytic enhancement effect of ash componets have been clarified by Kashiwaya et. al. [6]. Although degradation of coke in blast furnace has been examined recently[7], however, the degradation of coke after the reaction with C02 has not been well clarified yet. In the present work, the metallurgical coke specimen was heated in N2 and C02 and the reaction mechanism and degradation behavior after the reaction was investigated."

Jan 1, 2000

By V. Blet

Rare earth elements (REE) are regarded today as highly critical raw materials but currently lack suitable recycling processes. A combined hydro- and pyrometallurgical process aimed at REE recovery from used NdFeB permanent magnets was recently developed by the CEA. The process integrates the physico-chemical treatment of magnets, followed by a solvent extraction step for the recovery and intra-REE separation using a selective extractant. A subsequent pyrometallurgical treatment via molten chloride salt electrolysis allowed the isolation of pure Dy metal. Technical-economic assessment and life-cycle analysis were also conducted. Following this first successful demonstration, a new project aimed at the recovery of REE from end-of-life nickel-metal-hydride batteries is currently being developed in association with industrial and academic partners. The project aims at evaluating from an experimental and economic perspective different processes converging at the production of value-added products such as cermet materials for catalytic applications, purified REO concentrates, or metallic alloys.

By Jorge Alberto Soares Tenório

Household zinc based batteries contain some heavy metals such as zinc, manganese and mercury. There is a large effort from manufacturers in order to eliminate the last one. As a municipal waste, the disposal of batteries has become an increasing worry. The aim of the present work was to characterize dry batteries scraps, and establish a flowsheet for their processing. This was done using unit operations of mineral processing and parameters and yields of each stage have been defined. Such procedures have been chosen due to their low cost. The operations were hammer mill grinding, size separation, magnetic separation and specific weight separation in water. The characterization step was done through chemical analysis and x-ray difiactometry. After size classification, it was verified that 76.6% of the total amount of zinc was over 1.70mm. This fiaction was constituted basically of zinc and some coarse pieces from the steel body, paper and plastics. This fraction was submitted to magnetic separation followed by specific weight separation in water. A visual examination showed that during the grinding process, graphite was concentrated in the finer fractions. Manganese concentration in the fractions over 6,35mm was less than 2%. This means that there was low contamination by the paste in this fraction. It was due to the entrapment of the paste by steel scraps (from the body) and zinc (from the cup) during grinding.

Jan 1, 1999

By Rodney L. Williamson

Optimal estimation theory has been applied to the problem of estimating process variables during vacuum arc remelting (V AR), a process widely used in the specialty metals industry to cast large ingots of segregation sensitive and/or reactive metal alloys. Four state variables were used to develop a simple state-space model of the V AR process: electrode gap (G), electrode mass (M), electrode position (X) and electrode melting rate (R). The optimal estimator consists of a Kalman filter that incorporates the model and uses electrode feed rate and measurement based estimates of G, M and X to produce optimal estimates of all four state variables. Simulations show that the filter provides estimates that have error variances between one and three orders-of-magnitude less than estimates based solely on measurements. Examples are presented that verify this for electrode gap, an extremely important control parameter for the process.

Jan 1, 2001

By Emmanuel N. Zevgolis

After the Krupp-Renn process was shown to be unsuitable for treatment of the Greek nickeliferous laterites, the LM process was developed. It involved roasting reduction up to metallic iron in a Rotary Kiln (R/K) and smelting in an Electric Furnace (E/F). Ferronickel (with 15% Ni) produced in the E/F, was upgraded to 90-95% Ni in an 02 converter. Raw Ni was then electrolyzed to pure Ni. The LM process was not applied for very long however, due to various problems. So, the Larco process was developed, i.e., pre-reduction in R/Ks, smelting of the calcine in E/Fs for ferronickel production (15% Ni) and enrichment to 20% Ni, in an O2 converter. Until now, many technological improvements have been invented and applied or adjusted to the process, which have made it a fully reliable and competitive one. sohe of the improvements were the invention and application of a new granulation process for liquid ferronickel, the modification of the existing R/Ks, E/Fs and converters and the design of new ones, and others that are described in the paper. Keywords: Ferronickel, metallurgy, laterites, LM process, Larco process

Jan 1, 2004

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By Takahiro Furuzono

Saganoseki Smelter and Refinery of Pan Pacific Copper Co., Ltd. started treating copper anode slimes using a unique hydrometallurgical process in chloride media in 1997. The process comprises the following stages, decopperizing, wet chlorination, solvent extraction for gold, silver chloride reduction, and separate reduction stages that treat the gold extraction raffinate with sulfur dioxide gas. Precious metals and rare metals in the copper anode slimes are dissolved in an aqueous solution of hydrochloric acid by oxidative leaching, which is termed wet chlorination. Gold is efficiently extracted from the chlorination liquor by dibutyl carbitol in the solvent extraction stage. Gold is reduced by oxalic acid from goldloaded dibutyl carbitol and recovered as gold powder. The gold powder is cast directly into granules or ingots of more than 99.99% purity without electrorefining. Selenium is recovered as a selenium residue by reduction with sulfur dioxide gas and refined through vacuum distillation. The plant was designed to process 132 tonnes of copper anode slimes per month and has a current capacity of 206 tonnes per month due to several enhancements. Compared with the conventional process, the hydrometallurgical process described here provides some advantages, in particular, a higher product quality, shorter gold-retention time, and reduction in environmental load.

By Donna Guillen, Matthew Lehar, Sebastian Freund, Jennifer Jackson, Helge Klockow

"Research and development is currently underway to design an Organic Rankine Cycle (ORC) system with the evaporator placed directly in the hot exhaust stream produced by a gas turbine (GT). ORCs can be used to generate electricity from heat that would otherwise be wasted, thus producing carbon-free energy. In conventional ORC configurations, an intermediate oil loop is used to separate the hot gas from the flammable working fluid. The goal of this research effort is to improve cycle efficiency and cost by eliminating the pumps, heat exchangers and all other added cost and complexity of the additional heat transfer loop by developing an evaporator that resides in the waste heat stream. Direct evaporation – although simpler and less expensive to implement than indirect evaporation of the working fluid – has historically been avoided due to a number of technical challenges imposed by the limitations of the working fluid. The high temperature of the hot exhaust gas may cause decomposition of the organic working fluid and safety is a major concern due to the high flammability of some of these working fluids. The research team has addressed these challenges and developed a new direct evaporator design that can reduce the ORC system cost by up to 15%, enabling the rapid adoption of ORCs for waste heat recovery. The ORC system is intended to integrate with the GT either as a retrofit or to be marketed as a single package, thus maintaining the manufacturer’s warranty.IntroductionWaste heat from turbines and engines used in industrial applications along with waste heat from industrial processes are exceptionally abundant sources of energy. If even a fraction of this waste heat could be economically converted to useful electricity, it would have a tangible and very positive impact on the economic health, energy consumption, and carbon emissions in the U.S. manufacturing sector. Land-based gas turbines are used in a broad range of applications to produce both shaft and electrical power. Most commonly known for generating electricity either as peaking units or as base load units, they are also used to directly drive pumps, compressors or other machinery requiring shaft power. Simple cycle gas turbines have the advantage of a short startup time relative to coal-fired and nuclear units, however, they incur a significant penalty on their efficiency. Large frame gas turbines usually are combined with bottoming steam-based Rankine cycles to increase the overall efficiency of the system and thereby improve their cost performance. Small-frame gas turbines with exhaust temperatures around 500°C could in principle benefit from steam bottoming cycles, but rarely use them in practice because of the high capital cost of the steam system. Particularly for base load small frame gas turbines, akin to those used in pipeline applications, an increase in efficiency is highly desirable."

Jan 1, 2011

By Michael I. Morris

The U.S. Department of Energy's (DOE's) Transuranic and Mixed Waste Focus Area (TMFA), funded from fiscal year (FY) 1996 though FY 2002, was tasked with finding solutions for the mixed waste treatment problems of the DOE complex. During TMFA's initial technical baseline development process, three of the top four technology deficiencies identified were the need for amalgamation, stabilization, and separation/removal technologies for the treatment of mercury-contaminated mixed waste. The Mercury Working Group (HgWG), a selected group of representatives from DOE sites with significant mercury waste inventories, assisted TMFA in soliciting, identifying, initiating, and managing efforts to address these areas. Solicitations and contract awards were made to the private sector to demonstrate both the amalgamation and stabilization processes using actual mixed wastes. The goal was to develop separation and removal processes that will address DOE's needs. This paper discusses the technology selection process, development activities, and the accomplishments of TMF A through these various activities.

Jan 1, 2003

By Howard K. Worner

"In a rewarding career spanning nearly two thirds of a century, the author has worked at the frontier of such diverse fields as the creep of metals, structure properties and production of novel dental and surgical materials, molten salt electrolysis for titanium production, greatly improving the productivity of large iron blast furnaces and of oxygen steelmaking. While each of these has given great satisfaction, special thrills have derived from the development of new methods for the continuous production or refining of both ferrous and non ferrous metals. A rewarding segment was the evolution of various aspects of WORCRA technology. Unfortunately, several of these inventions have been ""ahead of their time"". Introduction""I am greatly honoured by the convening of this meeting to recognise my contributions to pyrometallurgy. My appreciation is the greater because this is the third Howard Worner Symposium; the first took place in the University of Newcastle in 1988, close to my 75th birthday. It was arranged by the local branch of The Australasian Institute of Mining and Metallurgy with the theme, ""Frontiers in Pyrometallurgy"". The second was organised by the University of Wollongong in conjunction with the Australian Academy of Science and the Australian Academy of Technological Sciences and Engineering; it celebrated my 80th birthday and, at my request, covered a broad range of topics under the heading of ""Recent Advances in Science and Technology"". Now, this very international meeting on ""Injection in Pyrometallurgy"" has been convened by the G K Williams Co-operative Research Centre for Extractive Metallurgy in my alma mater. I am both delighted and honoured that the cosponsors are the TMS (USA) and ISIJ (Japan).Dr Madhu Nilmani consulted me about the field to be covered and I readily concurred because ""injection"" has been of keen interest to me since the beginning of the 1960s when I began my pioneering work on sequential oxygen (or air) injection into flowing streams for both refining of blast furnace hot metal to steel and for the continuous smelting-converting of copper and nickel."

Jan 1, 1996

By J. E. Clemson

The Black Pine sediment-hosted, disseminated gold deposit is located in Cassia County, Idaho. Gold mineralization occurs in flat-lying zones 50 to 100 feet thick. Total geological ore reserves are 5.6 million tons grading 0.049 oz/t. Ore types include: non-carbonaceous, oxidized ore; carbonaceous, sulfide ore; and carbonaceous, partly oxidized ore. In the oxidized ores, native gold grains commonly occur in porous hematite pseudomorphs that have replaced disseminated framboidal and euhedral pyrite, and this gold should be readily leached by cyanide solutions. Approximately 4 % of the native gold observed in the oxidized ores is locked within gangue and may be refractory to cyanide solutions. Native gold has not been observed in the unoxidized samples, all of which are characterized by primary sulfides. It is suspected that the bulk of the gold mineralization in the sulfide ore occurs as submicroscopic particles within pyrite and will be refractory to cyanidation. It is believed that much or all of the gold observed in the oxidized samples was originally in pyrite but was released and re-precipitated during oxidation. The degree of oxidation of the pyrite and the presence/absence of preg-robbing carbonaceous material is used as a guide in delimiting zones of mineralization amenable to heap leaching.

Jan 1, 1988

By S. Ajima

The Naoshima Smelter and Refinery is the most important copper operation of Mitsubishi Materials Corporation. There are a Mitsubishi Continuous smelter and a conventional type of copper tankhouse. The continuous smelter with 240,000 mtpy of anode production was commissioned in May 19914 replacing two existing smelters, i.e an original Mitsubishi Process line and a conventional reverberatory furnace line. In July 1992, the copper tankhouae was expanded for the purpose to close the gap of production capacity between the smelter and the tankhouse. The cathode production capacity was increased from 13,800 to 15,800 mtpm. By these plant modifications, the distribution of minor elements was significantly changed and the impurities load is getting on increase reflecting recent shortage of clean copper concentrates supply. The paper discusses the distribution of minor elements and the impurity control strategy at the smelter end the refinery.

Jan 1, 1995

By Huimin Lu, Min Li, Jinghua Zou

"Zeolitic imidazolate frameworks (ZIFs) are new type of porous materials, form inerratic polyhedral in three-dimensional with large cages and small apertures, and appear structural diversity. Their hole size can be adjusted. These materials have high selective adsorption capacity to carbon dioxide. In this paper, zeolitic imidazolate frameworks were synthesized by solvothermal synthesis method with dimethylformamide (DMF) as solvent and structuredirecting agent, divalent metallic ions as cation, and imidazole as ligand. The crystals were characterized with XRD, SEM for their crystal structures and physical properties, the adsorption of the crystals for carbon dioxide was also tested, and the result suggests that these porous materials have a capacity of 1.35ml/g for storing carbon dioxide at 273 Kelvin under ambient pressure.IntroductionGlobal warming caused by the increase of carbon dioxide in the atmosphere has become one of the main environment problems, contemporary research has focused on ways to slow or stop this trend. CO2 capture has attracted attention due to the potential to trap and sequester large amounts of CO2 from concentrated sources such as power plants [1]. Traditional technologies in capturing CO2 include absorption by aqueous amines [2]. However, utilization of this process is energy intensive and expensive. Carbon dioxide storage materials investigated so far can be divided into two categories: chemical storage adsorbents and physical storage media [3]. The first kind of materials can chemically adsorb carbon dioxide within their structures and need thermal energy to release the adsorbed carbon dioxide. The examples of the chemical adsorbents include aqueous amines, gas-hyperbranched aminosilicas [4]. The physical adsorbents store carbon dioxide by physical adsorption of carbon dioxide at elevated pressure and release the adsorbed carbon dioxide at low pressure. The physical adsorbents that have been investigated for carbon dioxide storage include zeolites, carbonaceous materials and other porous materials. Until recently, a new type of microporous material, known as zeolitic imidazolate frameworks (ZIFs), has been reported as promising adsorbents for carbon dioxide storage [5 ~ 10]."

Jan 1, 2010

By J. D. Budai, D. H. Lowndes, D. P. Norton, D. K. Christen, B. C. Chakoumakos, J. R. Thompson, B. C. Sales

"Artificially-layered structures, consisting of (Sr,Ba,Ca)CuO2 layers in the tetragonal, ""infinite layer"" crystal structure, have been grown by pulsed-laser deposition. Superlattice chemical modulation is observed for structures with SrCuO2 and (Sr,Ca)CuO2 layers as thin as a single unit cell (~3.4 Å). In addition, novel thin film superconductors were formed by using the constraint of epitaxy to stabilize SrCuO2/BaCuO2 superlattices in the infinite layer structure. Using this approach, two new structural families, Ba2Srn-1CUn+l O2n+2+ d) and Ba4Srn-1CUn+3O2n+6+ d, have been synthesized which superconduct at temperatures as high as 70 K. These results represent not only the synthesis of new structural families of superconductors, but also demonstrate that pulsed-laser deposition and epitaxial stabilization can be effectively used to engineer artificially-layered thin-film materials.Advances in the understanding of epitaxial thin-film growth of the cuprates have heightened interest in creating artificially layered superconductors.(1-3) The layered structure of the copper oxide superconductors opens the possibility of forming novel materials by carefully controlling the epitaxial growth of sub-units of the crystal structures. Thin-film growth methods offer unique opportunities for the atomic engineering of new high-temperature superconducting (HTSc) materials through the ability to form artificially layered crystal structures.(4,S) Moreover, the surfaces of single-crystal substrates provide an ""atomic template"" that can be used to stabilize epitaxial films in metastable crystal structures.An important development in forming new HTSc compounds by artificially-layered epitaxy has been the epitaxial growth of (Sr,Ca)CuO2 films in the so-called infinite layer structure.(6-17) This material, which can be considered the parent compound of all of the copper oxide superconductors, has a relatively simple, layered structure consisting of CUO2 planes separated by planes of alkaline earth elements.(18) Bulk synthesis of (Sr,Ca)CuO2 with the tetragonal, infinite layer structure generally requires the use of high pressure and high temperature bulk processing techniques.(19-24) However, recent experiments show that this metastable compound can be epitaxially stabilized at less than atmospheric pressure, resulting in the growth of tetragonal (Sr,Ca)CuO2 single crystal thin films of the infinite layer defect perovskite structure by pulsed-laser deposition (PLD) over a wide range of growth conditions.(6-17)"

Jan 1, 1994

By J. W. Matousek

Cobalt behavior in pyrometallurgical processes is traditionally analyzed using slaglmatte distribution coefficients as functions of matte grades or matte iron contents. L(s/m) = (%Co) I [%Co] = f [%CuNi] or f [%Fe] The method is inconvenient to use in predictive mass balance work because of the interdependence of assays and mass quantities. An alternative procedure is proposed based on cobaltliron ratios for slags and mattes: Js = (%Co) / (%Fe), Jm = [%Co] / [%Fe], and J, = b + m [Jm]

Jan 1, 1993

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 C. Peter Hayes

The world continues to change and with it the supply of minerals and metals, the location of centres of production of primary metal and the increasing levels of metals and materials recycling. New technologies are being developed to meet the ongoing search by industry for lower costs, cleaner production and new markets. To keep abreast with these changes, and to utilise fully, the potential benefits of these technical advances, the industry will need a professional workforce having different knowledge, skills and professional attributes than in the previous millennium. What are these skills and attributes? How to best attract and develop the metallurgists of the future, and provide for the ongoing educational and research needs of the industry?

By KNona C. Liddell

The ion interaction model Pitzer proposed twenty years ago is today the most widely used method for calculation of osmotic coefficients and electrolyte and single ion activity coefficients in aqueous solutions. This is due in part to the accuracy of the results that have been obtained for many concentrated electrolytes. An additional factor is that, compared to alternative activity coefficient models, there are many more parameter values available for the Pitzer equations. The important features of this model are reviewed. Published parameter values for Co, Ni, Cu, Zn and Fe are tabulated, and applications of interest in the aqueous processing of these metals are described.

Jan 1, 1993

By Baozhong Zhao

The direct smelting of copper concentrates to copper metal in a single furnace offers environmental and energy advantages over conventional two-stage copper smelting processes. However, the direct copper making results in unacceptably high level impurities (As, Sb and Bi) in the anode copper. Experimental studies have shown that it is possible to remove these impurities from molten copper by injection of sulfur-hexafluoride. This paper discusses the experimental findings on the influence of various factors on the rate of removal of impurities, such as the impurity inter-effects, initial oxygen content in the metal and injection rate of SF6.

Jan 1, 1995

By Luis W. Pommier

The developed processes, the subject of this paper, extract the hydrocarbons, halogenated organic compounds and metal contaminants from hazardous soils, rendering them non-hazardous and ready to be placed back on the ground. The processes first segregate a non-contaminated fraction from the contaminated soil. This initial task is performed using available minerals processing technology: sizing, gravity separation, magnetic separation, froth flotation, etc. The remaining contaminated fraction, is submitted to two leaching operations for the removal of organic and metal contaminants, whenever both are present or to a single leaching operation if only one type of contaminant is present. The decontaminated soil fraction is mixed with the non-contaminated fraction and is placed back on the ground. The leaching liquors, used at neutral pH, are non- hazardous. After decontamination the liquids are processed to extract the contaminants, now valuable materials, for commercialization. Organic contaminants are removed by distillation of the solvents. The metal contaminants are precipitated in their oxide form. In both cases the regenerated solvents are recycled. The decontamination processes are economically competitive with transportation and disposal of the soils to permitted facilities for hazardous materials, and most importantly the developed processes remove the liabilities from the Responsible Parties. The law establishes that these liabilities do not disappear with either fixation nor with transportation and disposal since the environmental liabilities are of the ? cradle to grave? type.

Jan 1, 1994