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By Tianming Sun, Gabriella Tranell, Ragnhild E. Aune, Mark William Kennedy

Rare Earth Elements (REEs) are critical for the production of many advanced materials and products. Mining and primary production of REEs are generally associated with significant environmental impacts. By recovery of REEs from secondary sources, through recycling or as a byproduct, the adverse environmental impacts may be partly avoided. In the present study apatite concentrate originating from iron ore beneficiation done by LKAB in Kiruna, Sweden, is explored as a possible source for REEs. The composition and distribution of the REEs within the concentrates are studied using ICP-MS, XRD and SEM-EDS/EPMA, as well as the melting point and heat of fusion using DTA-TGA-MS. The behavior of the material during melting has also been studied through wetting and slag saturation experiments. The overall aim of the study is to evaluate the implications for future smelting experiments aimed at concentration and recovery of the REEs.

Jan 1, 2015

By Y. K. Rao

Relatively pure crystalline lead sulfate (PbSO4) can be produced by chemical vapor transport from an impure source such as the lead-acid battery paste or the roast-ore-leach-residue from a hy¬drometallurgical process-route. In a closed-reactor, transport of matter is induced by a tempera¬ture-gradient and the steady-state transfer rate can be calculated using the data on the standard free energies of formation for the species present and the pertinent binary diffusion coefficients. The present work focusses on chemical vapor transport in a tubular reactor (1.4-cm inner diameter x 10-cm long) with the source- and deposition-ends held at 850°C (T,) and 750°C (Td), respectively; PbC12(g) is the 'solvent' or 'transport agent' and NiSO4(s) placed in the source-zone -serves to maintain a sufficiently high S0,-potential such that the stability of the lead sulfate species is ensured. For the purposes of analysis, the gas-phase in the reactor is assumed to consist of eight species: H2O, PbC12, SO3, SO2. O2 HO, C12, and PbC14. The reaction between C12(g) and PbSO4(s) in the high-temperature source-zone produces PbCl2, SO2, and 02; four more reaction-equilibria in the same zone yield other species. In the low-temperature deposition-zone, reaction equilibrium involving PbC12, H2O, and SO, leads to the nucleation and growth of PbSO4 crystals; three other reaction-equilibria occur in this zone. By employing the virtual equilibrium state for the end-zones and coupling it to the Stefan-Maxwell diffusion equations for each of the gas species, the respective partial pressures for these, in the source- and deposition-zones, are computed at steady-state. From these data, the molar fluxes of PbCl2. PbCl4, and so forth, are determined. Allowing for the transport-enhancing effects of thermal convection, the net transport rate of lead (or PbSO4) is duly calculated for specified initial conditions. The predicted rates show very good agreement with measured rate data reported in the literature [ V. Plies, T. Kohlmann and R. Gruehn: Z. anorg. allg. Chem, 568, 62 (1989)

Jan 1, 1995

By G. Van Weert, A. van Sandwijk, O. W. J. S. Rutten

"Cathodic and anodic reactions in an acidic nitrate medium were studied in reference to the production of electrolytic manganese dioxide from pyrolusite' (Mn02) ores by reductive leaching. Two USA ores were investigated. The reductant for the pyrolusite ore is produced cathodically in an electrolytic cell and can either be nitrous acid (HN02) or nitric oxide gas (NO). In this work emphasis was placed on the nitrous acid leach. In a high-temperature leach in a nitrous/nitric acid medium, manganese and silver are solubilized and iron is not. Anodic electrowinning of manganese dioxide from the acidic manganese nitrate electrolyte yields flaky y-Mn02, similar to that produced from sulfate and chloride electrolytes. Cathodic regeneration of nitrorts acid was studied in a membrane cell in 1.0 M nitric acid and 0.0 to 0.1 M nitrous acid on a' platinized titanium cathode. At cathode potentials ranging from +950 to +700 mV (SHE), cathodic reduction to nitrous acid takes place, at cathode potentials < +700 mV, cathodic reduction of nitrous acid to nitric oxide takes place. A conceptual process is presented and discussed.IntroductionManganiferous-silver oresLarge reserves of manganiferous-silver ores are present in the Southwestern United States and Latin America. These ores are generally refractory to hydrometallurgical methods of treatment, due to the insolubility of the higher oxides of manganese (Mn 4+) in all common lixiviants such as cyanide solutions, dilute sulfuric acid, nitric acid, ammonia, salt solution, thiosulfates, etc. The silver is either bound by the insoluble manganese, or is rendered inaccessible to cyanide leach solution by the surrounding manganese mineralization.Higher oxides of manganese will dissolve if they are first reduced pyrometallurgically to manganous oxide (Mn2+). This is a widely used pretreatment for manganese dioxide ores and subsequent dissolution in sulfuric acid is common. In order to avoid the pyrometallurgical pretreatment with its large energy requirements and gaseous emissions, fully hydrometallurgical processes have been proposed. These processes are based on the presence of a reductant in solution, in order to reduce the insoluble higher oxides of manganese to soluble lower oxides. Aqueous S02 has been proposed and tested on industrial scale by the U.S. Bureau of Mines. After washing, silver could be extracted by cyanidation. The neutralization of the pulp prior to cyanidation however causes problems in filtration and the reagent consumptions are high [1]. More recently, acidified thiourea and bacteria were proposed for the solubilization of both manganese and silver in a single leach step. High extractions were obtained, but drawbacks of these methods are high reagent consumption or slow kinetics [2,3]. For the options of manganese recovery from the leach filtrate, precipitation with persulfate or ammonium carbonate and ion exchange have been proposed. The proposed options for silver reclaim are precipitation with either zinc or Na2S and adsorption onto activated carbon."

Jan 1, 1997

By D. Doungdeethaveeratana

The extraction kinetics in a novel solvent extraction process have been investigated. In this process, the liquid-liquid emulsion is generated by bottom gas injection into countercurrently flowing aqueous and organic phases. This process has a number of advantages over the mixer-settler unit or the spray column in terms of simple equipment configuration, without any mechanical moving parts, and the ease of cleaning and process control, while providing a sufficiently large interfacial area for rapid mass transfer. The overall rate increased with increasing gas injection rate and height of the aqueous phase but decreased with increasing injector diameter at the same gas injection rate. The variation of the overall rate constant was correlated against a set of dimensionless numbers, representing the operating conditions. Extraction rates and efficiencies comparable to those in a mechanically generated emulsion were attained in this new process.

Jan 1, 1998

By R. F. Hammen

Heavy metal contamination of water is a problem of immense national and international proportions. However, effective cleanup is complicated both by the toxicity and the low concentrations of metals in wastewater streams. Using high performance chelation chromatography, the solid phase extraction and purification of extremely dilute metals from water was highly effective. The process is based on selective displacement of metals from a chromatographic column containing a chelating resin. The resin is characterized by extremely efficient adsorption kinetics which allow rapid and complete removal of the metals.

Jan 1, 1993

By J. R. Donald

Surface and interfacial phenomena play a significant role in refractory performance. For example, the wettability of the refractory material with slag, matte, and metal influences infiltration and interfacial reactions. Yet, very little fundamental information regarding the surface properties of refractory materials and slag is available. Thus, in the present work, the sessile drop technique incorporating a high temperature furnace equipped with X-ray fluorescope was employed to investigate the surface and interfacial phenomena of fayalite-type slags on solid alumina at 1200?C. The iron to silica (Fe/SiO,) ratios employed were 1.4 and 2.0, and the oxygen potentials used were log p02 =-11 and log p02=-9 atmospheres. The contact angle between the fayalite-type slags and the alumina were determined to be relatively low, at about 16.9 to 19.6 degrees under the experimental conditions. The surface tension of fayalite slag (Fe/SiO2=1.4) at an oxygen potential of log -11 was 0.298, which agreed with the work of previous researchers. The surface tension of the fayalite was observed to increase with time. The spinel FeAl2O4. was determined to be the product of the interfacial reaction, and 8.8 to 15.8 mass percent alumina was dissolved into the slag after 40 minutes.

Jan 1, 1996

By Ronald Erdmann

Today the BOF filter dusts and sludges are mainly dumped due to their zinc contents. By typically ranging from 2 to 5 % they prevent the filter dusts and sludges from beeing recycled via the blast furnace route. Based on the different discharge kinetics of Iron and zinc during the main blowing period In a bottom stirred BOF a simple and efficient system for recovery allow zinc fractions has been developed. The obtained material Is suitable for recycling without nsc of shell formation In the blast furnace. Different subsequent development steps have been performed. By starling with a very simple lime dependent model the sludge from the BOF off gas cleaning system was collected in two different sludge channel systems. This model based an the fact that most of the scrap based zinc Is discharged from the melt within the first eight to ten minutes of the BOF process. To Improve the system a spectroscope zinc sensor was Installed at the hot section of the off gas cleaning system to get more reliable informations on the actual zinc concentation of the BOF dust. By use of the system up to 50 % of the BOF sludge can be recycled.

Jan 1, 1995

By Kenneth L. Nash

The control of solubility of waste actinide ions, by conversion to highly insoluble mineral phases has been demonstrated in the laboratory. Actinide metal ions are removed from neutral pH solutions by a combined ion exchange-decomposition-mineralization process based on the application of the naturally-occurring hydrolytically unstable.polyphosphate organic compound phytic acid.

Jan 1, 1999

By Masami Taguchi

"It is found that lead monoxide, PbO, has an ionic conductivity, and the all solid-state electrochemical cell using this oxide as an electrolyte has attracted the attention of battery researchers. In this study, thin film PbO2/PbO/Pb solid cells were produced on glass substrates and their discharge properties were investigated. The acti.ve material for the positive electrode, PbO2, was obtained by reactive sputtering of a Pb target in oxygen plasma. The PbO electrolyte and the active material for the negative electrode, Pb, were vacuum evaporated from /3 -PbO powder and a Pb block, respectively. The open-circuit voltage of the cell agreed with the theoretical value based on the thermodynamic data, and the close-circuit voltage was improved by the addition of a univalent impurity such as sodium or potassium to the PbO electrolyte. The connection of the cells in series and in parallel produced a higher electromotive force and a larger capacity. Also, the charge-discharge cycling test revealed that the cell could be charged and function as a storage battery.IntroductionGenerally, the ionic conductivity of a solid-state electrolyte is lower than that of a liquid electrolyte near room temperature. This has been a serious obstacle to using such electrolytes in an electrochemical cell. However, some solid-state electrolytes, which can preferentially pass a specified ion and have high ionic conductivity, have been found. Lead monoxide, PbO, which is an oxygen ion conductor, is such an example (1)(2). If a solid-state electrolyte is adopted for use in an electrochemical cell the problem associated with a liquid electrolyte such as leakage can be alleviated. The cell structure also can be simplified, because the electrolyte plays the role of separator to prevent the active materials from mixing. Thus, physical vapor deposition technology may make it possible to develop a very thin film cell, which consists of only solid phases (3)(4). In this study, the thin film PbO2/PbO/Pb solid cell with a thickness· of only a few micrometers, in which all the constituents were systematically deposited on a glass substrate by reactive sputtering and vacuum evaporation, has been produced and the charge-discharge properties were investigated. An attempt was made to improve the discharge properties by doping impurities such as Na2CO3 and Sb2O3 into the PbO electrolyte. Moreover, the connection of the cells in series and in parallel to get a higher electromotive force and a larger capacity, and the charge-discharge cycling test to determine its use as a storage battery were carried out."

Jan 1, 2000

By L. Filip

The roast-leach-electrowinning (RLE) process for zinc was modified to treat two typical complex concentrates containing zinc, lead, copper, gold and silver. Laboratory testwork results indicated that the optimum roasting temperature ranged from 700 to 800°C, in order to produce acceptable residual sulfur levels. The calcined concentrate was subjected to a three-stage leach sequence. The resulting leach solution was purified by hematitic precipitation and directed to the recovery of copper and zinc by solvent extraction and electrolysis. Alkaline smelting and subsequent electrolytic purification recovered the lead and precious metals from the leach residue. A flowsheet was developed based on the laboratory testwork results, and demonstrated in a large-scale pilot plant. The recoveries produced during the pilot plant operation ranged from 90 to 92% for zinc and copper, 85% for lead and 90% for gold and silver, respectively.

Jan 1, 1999

By Gus Van Weert

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

Jan 1, 1996

By A. Mezei

A process has been developed to recover cobalt, gold and bismuth from the NICO deposit in Canada. The process consists of a bulk rougher flotation followed by an optional separation by flotation to produce a bismuth concentrate and a cobalt concentrate, grading on average 12.8 % Bi and 1.8% Co, respectively. Cobalt is leached by pressure oxidation at 97% efficiency, producing a pregnant solution suitable for further processing. Before optimization, about 38% of the bismuth is recovered in the selective concentrate, wherefrom it is recovered by ferric chloride leaching followed by cementation, at overall efficiencies exceeding 98%. The gold is recovered from the cobalt and bismuth leach residues by cyanidation, at 95% efficiency. Previous work described the results of the leaching of the concentrates, recovery of gold (Part I) and the recovery of bismuth (Part 11). This work describes the results of the cobalt recovery testwork and the resulting conceptual flowsheet. The sulfur dioxide-oxygen system was the most efficient for the oxidationlprecipitation of iron and arsenic from cobalt bearing pregnant leach solutions, producing purified solutions assaying <1 mg/L As and <8 mg/L Fe. The efficiency of cobalt solvent extraction (from the resulting purified PLS containing about 1 g/L Co) ranged from 9 1 to 98%; the co-extractions ranged from 88 to 100% for copper, from 28 to 33% for magnesium, from 6 to 7% for calcium and from 96 to 98% for zinc. Sulphide precipitation processes (using either sulfur dioxidelelemental sulfur or sodium sulfide) produced residual copper concentrations in the cobalt strip solution ranging from 0.1 to 2 mg/L Cu. About 90% of the calcium and magnesium were separated by scrubbing the organic with cobalt sulfate, producing residual concentrations of 12 mg/L Ca and from 180 to 330 mg/L Mg in typical feed solutions directed to cobalt carbonate precipitation tests. Cobalt carbonate precipitation efficiencies ranged from 75 to 78% when calcium and magnesium co- precipitations were restricted from 8 to 17% and 0.3 to 0.4%, respectively. The limits required by most stringent specifications on commercial grade cobalt carbonate products were met or exceeded.

Jan 1, 2002

By Ko-ichiro Ohno

It is recently recognized that the iron reduction and melting as well as the slag separation of a composite of granular iron ore and coal are completed in a very short period of about 10 minutes when the composite is rapidly heated up to approximately 1673K. These phenomena are expected to be applied to a new iron-making process. The mechanism of iron ore reduction and iron-slag separation during rapid heating has not yet been revealed and the fundamental research has just started. Carburization of the reduced iron is regarded as one of the most important steps in this process. In the present work, the composite was prepared from four kinds of coal or graphite as a carbon source and electrolytic iron powder as a completely reduced iron ore. The temperature at which the liquid formation and iron carburization occurred was monitored. Direct observation of smelting reduction behavior was made by a confocal laser-scanning microscope combined with the infrared image-heating furnace to clarify the effect of molten ash on iron carburization. It was found that the meltdown temperature of composite became lower as the melting temperature of coal ash decreased. From the observed result, it was presumed that the liquid slag would act as an important media for the carbon transfer from coal to iron. The carburization mechanism during the smelting reduction was estimated as follows. When slag containing iron oxide melted down and contacted carbon, iron oxide in the slag was reduced and the formation of the metallic iron particle as well as the its carburization occurred simultaneously at the slag-carbon interface. Carburized iron particle was carried from slag-carbon to slag-iron interfaces due to the slag convection flow caused by the difference of the interfacial tension between the carbon-slag and iron-slag interfaces. Carburization of reduced iron could proceed with a repeat of the above-mentioned process.

Jan 1, 2003

By Pedro A. Netto, Giulio R. Altoé, Sergio N. Monteiro, Ygor M. Moraes, Frederico M. Margem, Gabriel O. Glória

Since environmental issues are becoming more and more important Worldwide. Nowadays, Natural fibers are been used to substitute the synthetic ones. Although PALF fiber is an important natural fiber and its mechanical Properties surpass in various aspects some other lignocelluloses fibers, such few studies have been conducted with the fiber obtained from leaf of PALF plant. In order to better evaluate the mechanical properties and possible applications, this paper aims to improve the elastic modulus of the PALF fiber by Weibull statistics, by evaluating their mechanicals properties and possible applications. The fibers were divided in diameter intervals and the tensile strength and elasticity modulus were measured in each range. The fractured surface was examined using scanning electron microscopy. The results, interpreted by the Weibull statistical method, showed a correlation between the fiber elastic modulus and its diameter.

Jan 1, 2015

By David B. Dreisinger

Mass and heat balance modeling is a powerful tool for the design and analysis of hydrometallurgical process flowsheets. In this first of two papers, we examine the basic fundamentals of mass and heat balance modeling, and apply these concepts to several flowsheets using a simple spreadsheet model. In this way, we aim to demonstrate how such models are not only easy to construct, but can also be indispensable for comparing various flowsheet alternatives, for making rational economic decisions, and for developing a basic understanding of existing process behaviour.

Jan 1, 2002

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus, The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn3O4) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6,7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn)04 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10.5 m2/s range. The pore size was mainly between 0.1 and 10 um,

Jan 1, 2003

By Jaroslav Horskoý, Miroslav Raudenský, Bogdan Filipic, Božidar Sader

This paper describes main elements and practical use of the computational system for automated setting of optimized casting conditions in the continuous casting of steel. The system consists of the heat transfer model of the process, empirical metallurgical criteria, and optimization algorithm. The physical model of the, strand temperature distribution relies on the classical Bennon-Incropera mixture continuum formulation for the convective-diffusive heat transport. Fluid flow effects are considered through enhanced thermal conductivity of the liquid phase. The model is solved by the operator-splitting Crank-Nicolson finite volume version of the Voller-Swaminathan scheme. The solution procedure is coupled with the IDS solidification analysis package. Boundary conditions for the strand cooling rely on combination of the generic and plant-specific mold, spray, and roll heat transfer coefficients ' by coping the effects of the casting speed, casting temperature, casting powder, mold oscillation mode, steel grade, water or air-mist spray type, running water, trapped water on the rolls, and radiation. The caster safety and productivity and the quality of the strand are related to nine empirical metallurgical criteria. The criteria ensure the caster safety and economy as well limit the internal, longitudinal, and transversal surface cracking possibility. The problem of finding optimum casting parameter values is stated as a minimization problem based on the analytical form of the cooling criteria evaluated from the steady-state temperature distribution of the strand. To solve the optimization problem, a genetic algorithm is employed. The algorithm explores process parameters settings heuristically by applying the principles of biological evolution. It starts with a random set of solutions and iteratively improves them through selection and variation. Solutions are evaluated by running the heat transfer model of the process and extracting the values of the empirical metallurgical criteria.

Jan 1, 2000

By P. Myllykoski, J. Nylander, A. S. Korhonen, J. Larkiola

The coefficient of friction and the deformation resistance have been determined from the measured rolling parameters by applying the Bland-Ford-Ellis rolling force model and the artificial neural network model (ANN). The dependence of friction on the parameters such as reduction, rolling speed, front and back tensions, contact pressure and deformation resistance have been studied by the ANN model. Measured data of over 10 000 coils have been used in the training stage. Various dependencies have been examined and the results show that the friction coefficient does not depend much on the rolling speed. The reduction and deformation resistance seem to have the strongest effect on the friction coefficient. A friction model based on neural computing has been included into the existing rolling force model.

Jan 1, 1994

By Simon Lekakh, Von Richards, C. Hank Rawlins, Kent Peaslee

"Batch aqueous leaching and carbonation tests were conducted using industrial steelmaking slags to determine the effect of carbonic anhydrase enzyme as a catalyst. Calcium leaching is a strong function of particle surface area, and the extent can be expressed as a function of time and particle size. Carbonic anhydrase did not affect the calcium-leaching rate, however, it did catalyze calcium carbonate formation to achieve a neutralization time near the theoretical rate. Additionally, carbonic anhydrase modified the precipitate morphology due to accelerated particle nucleation. Time controlled tests in which the pH dropped to ~6 decreased the amount of carbonate produced, and this effect was exaggerated by carbonic anhydrase, while pH controlled tests (>8.5) exhibited the highest rate of carbonation. Because the leaching rate was ~50% faster than the carbonation rate, a further increase in the amount of carbonation may be realized by using carbonic anhydrase however pH must be >10.3.IntroductionSteelmaking slag contains high fractions of alkaline earth oxide based phases (i.e., CaO and MgO) that exothermically form carbonates. Thus, it is being considered as a means of permanent carbon dioxide sequestration. At current U.S. steel production rates, approximately 13-17 million tons/year of slag are generated from basic oxygen furnace (BOF), electric arc furnace (EAF), and ladle metallurgy furnace (LMF) processes [1]. BOF and EAF slag is used as high quality mineral aggregate or cement clinker, while LMF slag, produced at ~15% the rate of BOF and EAF slags, has limited use as blast furnace flux or acid mine neutralization with the majority going to landfill [2]. Based on slag’s chemical nature and immediate availability as a co-product from steel production, the steel industry initiated a project to investigate hydrous carbonate formation in steelmaking slag as a method of sequestering carbon dioxide emitted in steelmaking offgas [3]. The goal of this project is to determine the reactor parameters suitable for the design of an industrial system for treating steelmaking offgas with raw or minimally processed slag."

Jan 1, 2009

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 fume less 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