Search Documents

By Grant Wallace, Rod James, Larry Twidwell, Ed Rosenberg, Courtney Young, Sean Dudley, Hsing-Hsin Huang, William Gleason, Jerome Downey

The use of applied chemistry in the production and optimization of leach solutions from Rare Earth Element (REE) ores and concentrates is being investigated. Ore and concentrate samples were characterized using scanning electron microscopy/mineral liberation analysis (SEM/MLA), X-ray diffraction (XRD), and Atomic emission inductively-coupled plasma spectroscopy (ICPAES). Multiple leach tests were performed to analyze the effects of temperature, residence time, and reagent concentration on the leaching of REEs. Analysis of leach solutions was carried out using ICP-AES. Modeling and statistical analysis of extraction behavior was carried out using DesignExpert 9. Modeling data for cerium extraction indicates that extraction is greatly influenced by temperature and reagent concentration, while leaching time plays a much less important role. Experimental design techniques are being utilized to optimize REE recovery. Results, conclusions, and directions for future studies will also be discussed.

Jan 1, 2015

By Timothy W. Ellis

"This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process scheme is discussed and a detailed description of several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this method to separate rare earth and other metal based materials will be given.IntroductionConcerns over the effects of waste materials in the environment has been one of the significant social hallmarks of the late 20th century. Essentially every industrialized country has had to incorporate the cost of waste material into the equation of production. Legislative initiatives have led to the passing of very tough laws, by historical standards, which govern the environmental impact of materials processing.Liquid-Liquid extraction is a very common unit operation normally using aqueous and/or organic based solvents. Early work at the Ames Laboratory focused on the use of this technique for the reprocessing of spent fuel from liquid metal breeder reactors by the use of metallic solvents. Recently, we have revisited this area as a means to recycle/reprocess several emerging rare earth based materials, although this method has a much wider range of application. The reinvestigation of this technology is particularly timely as hydrometallurgical based processes are coming under increasing scrutiny in the U.S.A. by the Environmental Protection Agency (EPA). Although technology currently exists to remove contaminants from aqueous based waste streams, often the application of such methods is expensive. With proper design and judicious selection of reagents liquid metal extraction can achieve a high recovery along with a benign waste stream.This process has several possible advantages over other technologies. First is the elimination of aqueous solvents. Therefore, problems associated with disposal or reprocessing of the aqueous carrier are eliminated. Second, with proper system design, very high separation coefficients can be obtained thus limiting the number of stages required. Third, metals are extracted from metals with a metallic product, thereby eliminating the need to re-reduce metal for oxides or other compounds which are the common output for aqueous based extraction procedures."

Jan 1, 1996

By J. L. Jambor

Previous crystal-structure determination of magnesian annabergite (Ni,MgMAsO4)2 8H2O indicated that ordering of Ni and Mg occurs in non-equivalent octahedral sites; such ordering supports the possibility of miscibility gaps on the Ni3(AsO4)2 8H2O -MgiAs04)2 8H2O. (annabergite-hornesite) join. In a predecessor study based on analyses of natural specimens, it was proposed that solid solution is incomplete both for annabergite-hornesite and annabergite-erythrite [Co, (AsO4)2 8H2O]. In the current study, syntheses by use of a slow-addition technique and aging of the precipitates indicated that the annabergite-erythrite solid solution is complete, and that no miscibility gap is present on the annabergite-hornesite join to at least 58 mol % Mg. Thus, interpretation of the compositions of these phases in oxidized mill-tailings impoundments can be done with the normal precautions for homogeneity, and without the added concern of the possible presence of miscibility gaps in the ternary system.

Jan 1, 1995

By Y. Ide, K. Kishitake

It is expected that an Al-Cr-N composite nitride film may have a higher resistance to oxidation at elevated temperatures than the well-known Ti-Al-N films. The formation conditions of Al-Cr-N films by a de reactive sputtering method and their properties were studied in this study. The films characterized with respect to their high temperature properties such as chemical composition, crystal structure, microhardness, wear and· friction. The crystal structure of the Al-Cr-N films changed from hexagonal phase to cubic phase with an increase in Cr content in the films. The resistivity to thermal oxidation of the Al-Cr-N films is superior to that of usual TI-Al-N films. A half of the friction coefficient in the Al-Cr-N film was obtained comparing with that in the ordinary TI-Al-N film at room temperature and the wear rate of Al-Cr-N film was 2 order smaller than that of TI-Al-N film. The Al-Cr-N films show a small friction coefficient at 500°C and then they are recognized to have good tribological characteristics.

Jan 1, 2000

By M. El Ganaoui, P. Bontoux

"A computational model to investigate solid/liquid phase change transitions for binary alloy under directional solidification is presented. Conservation equations are developed by using an homogeneous formulation. A second order accuracy method of time and space based on finite volume approximation has been evaluated by comparing results to spectral solution for time-dependent solutal convection developping in a melted alloy. For extended model to solid/liquid interface effects time amplification of solutal perturbation injected near the interface is described before considering solutal convection is melt.IntroductionThe enthalpy method gives a front fixing approach for energy equation without introducing coordinate transformation. The interfare position is recovered a posteriori [1]. A number of authors have extended this approach so as to include the convection phenomena within the two phase 'mushy region' [2, 3, 4, 5, 6].We have developed a time-dependent enthalpy-porosity formulation for directional solidification [4, 6, 8]. The interaction between solid and liquid phases is modelised by a Darcien type force in the phase change area. The behaviour of the melt is similar with the flow of an incompressible fluid in a porous medium. This force is proportional to the relative phase velocity. It corresponds to a damping force depending on the anisotropic permeability of the 'mushy zone'. The permeability depends on the liquid fraction and on the size of·solidification microstructures. An informative discussion of a new slant on the general approach of continuum mechanics needed to analyze the formation of mushy zone is given in [12]. The method is extended to the presence of species diffusion: the solutal Stefan condition which expresses the solute incorporation or rejection across the interface is accounted implicitly in a species equation valid in all the domain [14, 15]."

Jan 1, 2001

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction, The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory-scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the determination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the determined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors determining the time of reduction.

Jan 1, 2003

By E. J. Peterson

Oil shale retorting induces mineral and chemical reactions to occur on the macroscopic and microscopic levels in the kerogen-bearing marlstone. The nature and extent of the reactions is dependent upon process variables such as maximum temperature, time at temperature, atmosphere, and raw shale composition. This report describes the investigation of the mineral, chemical, and trace element release properties of spent shales retrieved from an experimental in situ retort at Occidental Oil Shale, Inc. 's Logan Wash site in Garfield County, Colorado. Correlation between mineralogy of the spent materials and the mobility of major, minor, and trace elements are indicated, and relationships with important process parameters are discussed. The progress .of carbonate decomposition reactions and silicat ion reactions is indicative of the processing conditions experienced by the shale materials and influences the mobility of major, minor, and trace elements when the solids are contacted by water. Shale minerals that are exposed to the extreme conditions reached in underground retorting form high temperature product phases including akermanite-gehlenite and diopside-augite solid solutions, kalsilite, monticellite, and forsterite. The persistence of relatively thermally stable phases, such as quartz, orthoclase, and albite provide insight into the extremes of processing conditions experienced by the spent shales. Leachate compositions suggest that several trace elements, including vanadium, boron, fluoride, and arsenic are not rendered immobile by the formation of the high-temperature silicate produce phase akermanite-gehlenite.

Jan 1, 1981

By Hang Goo Kim

A computer simulation has been carried out to predict the distribution behavior of minor elements such as Pb. Zn, Bi, Sb and As in recently proposed copper smelting and converting processes with submerged oxygen injection in which tonnage oxygen is used with a shielding gas. In this study the technique of stepwise equilibrium modeling was employed and some of the thermodynamic data were updated or reassessed. The volatilization and slagging of undesirable elements were investigated in copper smelting (steady-state) system, copper matte converting (batch) system, and the combined (smelting + converting) system at extremly high oxygen-enrichment levels. The predicted minor-element behavior under high oxygen- enrichment was compared with that in the Noranda process (normally 42% oxygen-enrichment in smelting and 24% in converting) and the reverberatory process using air. The effects of various operating parameters such as temperature, the final matte grade in smelting, the initial matte grade in converting and the O/Fe ratio in slag on the behavior of minor elements are discussed.

Jan 1, 1991

By D. J. Senor

Closed chamber incineration (CCI) is a novel technique by which irradiated nuclear graphite may be destroyed without the risk of radioactive cation release into the environment. The process utilizes an enclosed combustion chamber coupled with molten carbonate fuel cells (MCFCs). The transport of cations is intrinsically suppressed by the MCFCs, such that only the combustion gases are conducted through for release to the environment. An example CCI design was developed which had as its goal the destruction of graphite fuel elements from the Fort St. Vrain reactor (FSVR). By employing CCI, the volume of high level waste from the FSVR will be reduced by approximately 87 percent. Additionally, the incineration process will convert the Sic coating on the FSVR fuel particles to SiO2, thus creating a form potentially suitable for direct incorporation in a vitrification process stream. The design is compact, efficient, and makes use of currently available technology.

Jan 1, 1994

By Tao Xuea

Gold frequently occurs in nature in the form of a gold-silver alloy. Thus, investigation of the electrochemical behavior of gold-silver alloys in cyanide solution has practical significance. In this paper, the potentiodynamic method is used to determine the anodic polarization curves of gold-silver alloys (Au-10% Ag and Au-50% Ag) in cyanide solutions. To facilitate the interpretation of the results, complementary experiments conducted in NaOH solution in the absence of cyanide are also reported. The results for the Au-Ag alloys are compared with the polarization behavior of pure gold and pure silver. With the aid of potential-pH diagrams for the Au- and Ag-CN-H20 systems and electrochemical kinetics concepts, the dissolution mechanism of gold-silver alloys, the effect of the presence of silver on the cyanidation of gold, as well as the factors which control the anodic reaction rate are clarified.

Jan 1, 1998

By Marco Olper

After two years of extensive research a new and innovative modification to the CX-EW process has been exploited. This process, called CX-EWS, avoids completely all the critical aspects of the previous process which affected the cost of the energy, of the chemicals and of The maintenance of the insoluble anodes. All these benefits reflect a saving of about 30% of The operating costs compared to the present traditional production and allow for a total operating costs of less than 6.5 cts/lb. lead (net of raw material cost). With this new technology it is allowed for the first time the treatment in the same plant facilities of both primary lead sulphide concentrate and spent batteries. The paper describes the technical and economical aspect of the new process with a feasibility study for 150,000 t/y spent battery facility throughput.

Jan 1, 1995

By W. D. Cho

The slag chemistry in steel processing plays an important role in terms of the removal of impurities including alumina particles. In the present study, the dissolution of solid alumina particles in CaO-based fluxes at the temperatures between 1450 and 1550 °C has been investigated to determine dissolution kinetics and mechanism. Alumina particles were added directly in the slags and the size of alumina particles was measured as a function of time using optical and scaru;ling electron microscopes. The dissolution rate has also been obtained as a function of Si02, CaF2, MgO and MnO contents in the slags. The diffusion boundary layer between alumina and bulk slag phase has been observed and analyzed using SEM and EDX. In addition, some experiments have been performed for the dissolution of alumina in BaO-based fluxes.

Jan 1, 2003

By R. J. Dippenaar, W. H. Van Niekerk

"An injectable lime-based desulphurization reagent for the treatment of liquid iron was developed. Firstly, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na20 to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. Subsequently, pilot plant and full scale industrial injection trials were conducted. It was found that lime-based slags, containing Na20 and CaF2, are able to desulphurize liquid iron efficiently. By the injection of a lime based reagent consisting of 60% lime, 25% soda ash and 15% fluorspar at a rate of 7 kg reagent/ton hot metal, the sulphur level in the metal (115kg) was reduced from 0,07% to 0,01 % within 5 minutes. The lime-based reagent developed in this study was successfully injected, both from a metallurgical and from a pneumatic point of view, on an industrial scale. The mathematical model utilised in this study, can be used successfully to predict the course and extent of desulphurization by lime-based slags. IntroductionMainly due to environmental difficulties encountered with pure soda ash, dry slag formation with CaC2 and high cost when Mg are used as desulphurizers, much incentive exists for the development of an inexpensive, environmentally friendlier desulphurization reagent. As a first step in the development of such a reagent, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na2O to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. This was followed by pilot plant injection experiments in which the kinetics of the relevant desulphurization reactions were evaluated. Finally, full scale industrial trials were conducted. All three phases of the investigation will be discussed with the major emphasis being placed on the kinetic study."

Jan 1, 1996

By Brian G. Thomas

Quality problems in continuous casting of steel can be identified as they occur by monitoring mold signals (level sensor, thermocouples in the mold walls, friction etc.) and taking appropriate action (such as slowing casting speed, changing taper, changing a clogged nozzle, or later visual inspection of the surface for possible downgrading. Surface depressions and groups of deep oscillation marks form at meniscus and reduce local heat transfer as they move down the mold at the casting speed. This slows shell growth, increases shell surface temperature, and causes characteristic dips in mold thermocouple signals. More importantly, they are also associated with longitudinal cracks. Characteristic thermocouple signatures have been identified for many defects, including sticker breakouts, transverse depressions and deep oscillation marks, narrow-face bleeds, transverse comer cracks, longitudinal cracks, mold level fluctuation defects, and other problems. With the help of computational models, these mold signals should be used to troubleshoot defects, and to take appropriate corrective action. Keywords: Continuous casting, defect detection, thermocouple signals, on-line control

Jan 1, 2003

By M. Nilmani, H. Pham

"A mathematical model was developed for the dissolution of particles in gas-stirred liquid baths, linking the hydrodynamic flow field of the bath, the average particle trajectory and liquid-side mass transfer controlled dissolution kinetics. The model was validated by comparison with experimental data for the dissolution rates of urea particles in gas-stirred aqueous CaCl2 solutions measured during this study. The dissolution rates of urea. particles were measured using an image analysis system.The effects of operating conditions on the dissolution rates of urea particles were investigated. It was found that the key operating parameters influencing the utilisation efficiency of particles were the gas flowrate, particle diameter and lance submergence. An optimisation of the operating conditions for the model urea-aqueous CaCl2 system indicated that the utilisation efficiency increased with decreasing gas flowrate and decreasing particle size for a given lance submergence.IntroductionThe utilisation solid reagents in molten baths varies from one process to another, depending upon the rates and mechanisms of the reactions between the particles and melts, as well as the trajectory and residence time of the particles in the melts. Previous studies have not attempted to predict the utilisation efficiency of injected solids by coupling the motion of the particle with its dissolution rate. Instead, the particles have usually been assumed to remain suspended in the bath until completely dissolved, and the mass transfer coefficients were based on the average specific mechanical energy dissipation rates in the bath. Investigations of this nature relevant to the present study have been undertaken by Apelian et al. [1], Brucato et al. [2] and Langberg and Nilmani[3]. The objective of the present study was to develop a mathematical model, incorporating both the reaction kinetics between the particles and liquid and the particle motion simultaneously, to predict the dissolution rates and times of the particles. The mathematical model was validated by comparison with experimental dissolution rates of a cold model analogue system measured using an image analysis technique, and then applied to optimise the operating conditions in the model system."

Jan 1, 1996

By A. Patti, S. Reutzel, D. M. Herlach, L. Ratke, I. Egry

Cu-Co shows a metastable miscibility gap in the region of the undercooled melt. Undercooling of the melt below the binodal leads to separation of the melt into a Co-rich LI-phase and a Curich L2-phase. Experimentally, undercooling into the metastable miscibility gap is realised by means of electromagnetic levitation (EML), processing in drop tube (DT) and by melt flux embedding. As undercooling is large in these experiments, the velocity of the solidification front is high and the microstructure is frozen in instantaneously. Samples have been undercooled and solidified in the TEMPUS-facility (container less electromagnetic processing under weightlessness) during parabolic flight under reduced gravity conditions. Microstructures of solidified samples have been analysed and compared to those processed under gravitational conditions. The influence of convection on phase growth is much lower in reduced gravity. The microstructure shows spherical droplets of the minority phase, statistically dispersed in the majority phase.

Jan 1, 2004

By Emmanuel N. Zevgolis

In the present work, a reduction roasting experimental study of Greek nickeliferous laterite samples with a gaseous reducing mixture ? CO:N2- is presented. The effect of parameters such as temperature, ore grain size, and composition of the reducing mixture were examined. It is deduced that the reducibility of intermediate type laterite sample, where iron appears mainly in the form of goethite (a-FeOOH), is considerably higher than that of limonitic type laterite samples, where hematite (a-Fe2O3) is the predominant iron mineral phase. The degree of reduction of the limonitic type laterite samples does not exceed 50%, while it reaches 95% in the case of the intermediate-type laterite sample under the same experimental conditions. Increasing the temperature in the range 750-900°C does not considerably favor the reduction of the limonitic type laterites, whereas decrease of ore grain size of the limonitic-type ore samples and more intense reducing conditions increase the reduction. The considerably higher specific surface area values of the intermediate laterite samples, diminishes the effect of the ore grain size and this can be regarded as the critical parameter leading to the higher reducibility of this ore.

Jan 1, 2009

By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By K. E. Gonsalves, G. M. Chow

"Nanostructured powders (particle diameter of 1 - 100 nm) have uses in electronic, magnetic, structural, thermal applications as well as advanced processing of materials. Among many methods of making nanostructured powders, chemical routes offer many attractive features such as feasibility of cost-effective bulk quantity production, design of chemistry at the molecular scale, and chemical homogeneity of the powders. In this talk, two systems of chemically synthesized nanocomposite powders are presented, namely, granular magnetic materials of Fe-Cu and Co-Cu, and thermal-structural materials of AIN-BN. Synthesis and processing, characterization and properties of these materials are discussed.IntroductionNanostructured powders (particle diameter of 1 - 100 nm) are attractive materials because of many useful properties (e.g. catalytic, optical, magnetic etc.) and processing advantages (e.g. lower sintering temperature) [1]. There are many methods of making nanostructured powders, for example, physical and chemical vapor deposition, mechanical attrition, and solution chemistry [1, 2]. A common method of making composite powders involves the grinding, mixing and blending of constituents powders, but it has the limitation of inhomogeneous mixing. Chemical routes have many useful features. Using solution chemistry, precursors can be molecularly tailored and homogeneously mixed at the molecular level. The chemical approach may result in better properties of the final product. Compared to vapor-phase fabrication techniques, chemical routes are more cost-effective in producing large quantity of material. In addition, control of particle size, size distribution and stabilization of the nanoscale particles against agglomeration can be more effectively manipulated via solution chemistry.In this paper, we present an overview of some of our work in nanocomposite powders prepared by solution chemistry. Metallic systems of FeCu and Co-Cu, and ceramic system of AIN-BN are discussed. The powders were characterized using x-ray diffraction (XRD) , scanning electron microscopy (SEM), conventional and high resolution transmission electron microscopy (TEM, HRTEM), vibrating sample magnetometry (VSM), inductively coupled plasmaatomic emission spectroscopy (ICP-AES)."

Jan 1, 1994

By William Petruk

The capabilities of SEM/image analyzers for determining quantitative mineral data which have a bearing on extractive metallurgy have given applied mineralogy a new dimension. The capabilities include automatic mineral identification, unattended operation, search for rare minerals, and measurements of (1) mineral quantities, (2) grain and particle size distributions, (3) liberation characteristics of minerals in ground ores, and (4) mineral associations. Data on mineral quantities define the distributions of elements among minerals, provide background information on characteristics of the samples, and provide a data base for a mineral-materials balance. Size analysis data of the minerals in unbroken ores are used to predict the grind required to liberate minerals. Data on liberation analysis can be used in many ways. One application is to process the image analysis data for feed, concentrate and tails by a materials balancing technique to calculate the recovery of liberated and unliberated grains at each point in a circuit. The calculated recovery data define the behaviour of an ore in a concentrator, pilot plant or bench test, and indicate whether recovery improvements are possible and/or feasible for a particular ore.

Jan 1, 1991