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By E. James Quinn

Solvent extraction technology using EHEHPA (2-ethylhexyl phosphonic acid, 2-ethyhexyl mono ester) is the norm for industrial separations of rare earth elements. This process has some shortcomings, including a large number of stages compared to most SX processes and high acid requirement for stripping of the heavy rare earths. In this work, we examine a number of alternative mixed solvent extraction systems: (i) Mixtures of organophosphonic and phosphinic acids such as EHEHPA/Cyanex 272 or Cyanex 572; (ii) Ionic liquid mixtures of EHEHPA with quaternary ammonium chloride (Aliquat 336); and (iii) Mixtures of carboxylic acids for yttrium/lanthanide separations. We discuss and compare the efficacy of these systems with reference to the Nd/Sm separation, which is of industrial significance. Based on the extraction chemistry and the use of modelling tools to define the counter-current solvent extraction circuit, we present a techno-economic analysis of a separation plant and discuss the impact of various solvent systems on the capital expenditure (CAPEX) and operating costs (OPEX).

By A. Andreas Hejja

Flow of slag and settling of matte in slag resistance electric furnaces are discussed in conjunction with furnace geometries, stirring action of the electrodes, buoyancy and electromagnetic effects. The rectangular electric furnace was regarded as a channel reactor and the mode of slag flow as a channel flow. The flow is affected both by buoyancy and electromagnetic forces, however the effect of electromagnetic forces is minimal. The flow velocity is made up of two components; (i) that developed by the action of the electrodes, and (ii) the bulk flow velocity determined by the smelting rate and the volume of the reactor. Slag samples were taken from various depths of the molten bath and were analyzed microscopically to determine the size and distribution of matte particles, The action of the electrodes was described by a simple mathematical formula indicating a balanced settling rate in the area of electrode action.

Jan 1, 1996

By Gaballah Djona M.

Spent hydrorefining catalysts contain about 5 % of CoO and/or NiO, 12 % of MoO3 and up to 10 % of V205. They are generally supported by alumina and contain up to 25 percent of C, S and hydrocarbons. Such materials are potentially hazardous to the soil and to water resources. Selective chlorination of raw unroasted samples with Cl2 + air gas mixture had been investigated. At temperatures lower than 600 °C, it was possible to recover more than 90 % of nickel and cobalt chlorides, about 99 % of the molybdenum and up to 75 % of vanadium chlorinated compounds. CoCl2 and Ni/Cl2 were extracted from the chlorination residues by their dissolution with acidified water. Molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The chlorination of Al2O3 could be limited to less than 6 %. The scale up of this treatment was successful and a flow-sheet is proposed.

Jan 1, 1995

By T. Shoji

"The human history is characterized by social development based on mineral and energy resources, and many conflicts to take the resources by power. This is shown by not only world wars but also many local conflicts as well as international supremacy.IntroductionThe world population after B. C. 10000, which is summarized in several papers, is approximated by four straight lines on a semilogarithmic diagram as shown in Figure 1 [l]. The annual rates of increasing are 0.0041, 0.071, 0.53, and 1.85 % from the old and young periods. The boundaries among four periods are approximately B. C. 4600, AD. 1670, and 1930. The start of the second period seems to correspond to the beginning of agriculture and cattle breeding. Precisely speaking, the usage of natural energy resources such as woods and domestic animals already began, but is inferred to have become common after the age. The third and fourth periods are characterized by the common usage of coal and oil, respectivety. Not only energy resources but also mineral resources including gold, copper, iron and others are also important for the human history.Mineral and energy resources have supported the development of the .human civilization, and have caused many conflicts because of this reason. Every day newspapers report conflicts, such as Chechnya, East Timor and Ache. We can easily point out the facts that the conflicts closely relate to mineral and energy resources. Groznyj, Capital of Chechnya, is located on the western margin of Caspian oil field. Many mineral deposits occur in Kavkaz Mountains running south of Chechnya. Subsea oil fields occur in Timor Gap located between East Timor and Australia. Ache is also one of oil fields in Indonesia. It is very difficult to state present conflicts independently of a political view of point. For this reason let us try to historically review the relation between mineral and energy resources and international domination and conflicts [2] based on many papers [3]."

Jan 1, 2000

By K. D. Peaslee, V. L. Richards, C. H. Rawlins, S. N. Lekakh

"Steel-making processes generate carbon dioxide air emissions and a slag co-product. The aim of this project was to develop a functional sequestration system using steelmaking slag to permanently capture carbon dioxide emitted in steelmaking offgas. A possible parallel benefit of this process would be rapid chemical stabilization of the slag minerals with reducing swelling or leaching.This paper summarizes the original results of the project, including mineralogical and structural features of carbon sequestration with steel making slag, mathematical modeling of reaction phenomena using a modified shrinking core model, METSIM modeling of several possible industrial applications, a thermo-gravimetrical study of the reaction between slags and different gases, and design and testing for a lab scale apparatus consisted of two reactors.1. IntroductionThe U.S. produces 9-14 Mt of steelmaking slag annually, which represents approximately 10-15 wt. % of crude steel output.1,2 Primary uses for steelmaking slag include high quality mineral aggregate, Portland cement, unconfined fill, soil conditioning, and pH neutralization of abandoned mine drainage.3,4 The key factor prescribing slag use is the alkaline-earth metal (e.g. Ca and Mg) oxides content, which contribute to overall basicity and cementitious strength. However, as-produced steelmaking slag is chemically unstable. Calcium and magnesium oxides readily form hydroxides and carbonates through reaction with atmospheric gases. Both hydroxide and carbonate formation produce substantial mechanical swelling leading to heave failure in confined construction applications, thus many states dictate stockpile aging for 3-6 months prior to commercial use.5,6 Sequestration of carbon dioxide is a natural corollary to forced carbonation. The conversion of CaO/MgO to carbonates serves both to stabilize the slag, and permanently capture and store the CO2."

Jan 1, 2008

By J. A. Sekhar

Solidification processing/casting is increasingly being adopted as the preferred manufacturing technique for the fabrication of net shaped complex geometry components. Modeling of solidification processes is important both for design purposes as well as for understanding the physics of morphological evolution of the solidification microstructure. A fundamental aspect of such modeling involves the precise understanding? of heat transfer through the two phase solid/liquid region. A scheme to do this will be presented where the nonlinearity of the fraction liquid with change in temperature can be incorporated into the numerical calculations. The importance of properly accounting for the non-linear mushy zone will be discussed. Typical processes like squeeze casting and electromagnetic stirring will be discussed to illustrate how precise modeling of the solid/liquid region can aid in the calculation of accurate heat transfer coefficients for these processes.

Jan 1, 1990

By R. R. Odle

A laboratory and pilot-scale investigation of direct smelting of copper concentrates was conducted to determine the effect of concentrate analysis and the degree of roasting on the yield and quality of copper produced in a subsequent smelting step. A stoichiometric :mOdel of direct smelting is presented which predicts the? quantity of copper; slag, and white metal' prOduced'and the distribution of copper in these phases as a function? of the concentrate '(calcine) analysis.

Jan 1, 1983

By Albert F. S. Seboukens

A 5;6 MVA pyrometallurgical demonstration-scale pilot plant was commissioned at Mintek, South Africa, in 1994, using lead blast-furnace slag and coke as raw materials. The plant included a.d.c. power. supply, two plasma-arc furnaces' and an ISP lead-splash condenser. Slags containing typically 12 per cent zinc oxide and 3 per cent lead oxide are produced as a waste during the smelting of lead in a blast furnace. These slags are a potential: resource for the recovery of lead and zinc. During 1994, about 600 t of lead blast-furnace, slag was proceced through the pilot plant using the Enviroplas process. Zinc and lead oxides were reduced to their respective metals, volatilized, and collected in an. ISP lead splash condenser. Prime Western grade zinc and slags disposable in accordance with current US legislation, were produced. Zinc condensation efficiencies of about 80 per cent were achieved.

Jan 1, 1995

By Joseph Goodwill

1. PURPOSE The objective of this paper is to summarize a study undertaken by the EPRI Center for Metals Production (CMP). The overall purpose of the study was to identify electrolytic opportunities that might merit consideration for joint development by industry and EPRI. 2. SCOPE The electrolytic technologies of interest to this study include: Electrorefining, Electrowinning, and Fused-salt electrolysis. Recovery from primary, secondary, and waste materials were included in this effort; however, we excluded from consideration: Plating and coating operations, such as electrogalvanizing; Mining and milling operations in which electric energy is predominantly used for comminution; Electrothermal processes in which submerged-arc, open electric-arc, and plasma-based smelting processes use electric energy largely to provide a melting or refining ("heating") capability; and Aluminum electrotechnologies since these were the subject of a separate study (CMP 86-2). We recognize that there may be some "gray areas" between these excluded areas and the electrolytic sectors of interest. For this reason, a secondary criterium was used, namely, if the major use of electric energy was to extract or refine the

Jan 1, 1990

By Devon A. Hannan

Thermodynamic modeling calculations were undertaken for the recovery of mercury from HgTe using a vacuum retort reactor. However, discrepancies were noted in the available thermodynamic data which introduced uncertainty in the model results. Consequently, a series of transpiration experiments were first undertaken on the thermal decomposition of HgTe into an inert carrier gas stream according to the following reaction: HgTe(s) Hg(g) + Te(s) From the measured weight loss of the HgTe samples, the Gibhs free energy change for the above volatilization reaction was determined as a function of temperature. The experimentally determined Gibbs free energy values were found to be approximately 30% larger (more posi-tive) than the values available in databases such as HSC Chemistry. By conducting a second-law analysis on the experimental data, the heat of formation of HgTe at 298.15 K and the en-tropyat 298.15 K were determined, which then formed the basis for a new database for the modeling calculations. The results of this study showed that HgTe was more stable at elevated temperatures than was generally indicated in the literature. The new database is given in a for-mat for direct insertion in HSC Chemistry. Using the new database, modeling calculations were conducted to examine the effects of the re-tort pressure and the molar ratio of purge gas to HgTe on the volatilization of mercury from HgTe. A diagram is presented that shows the minimum temperature for 100% volatilization of mercury from HgTe as a function of retort pressure for different molar ratios of purge gas (N2) to HgTe. For example, it was found that the minimum temperature for 100% volatilization could be decreased by 175 K, at a retort pressure of 0.05 bar, if the molar ratio ofN2 to HgTe is increased from 1.0: 1 to 100.0: I.

Jan 1, 2003

By J. D. Miller

Low-level radioactive contaminated soils (10-500 pci/gm) created by defense-related activities at certain superfund sites, such as Nevada Test Site (NTS), is a current environmental concern. Many of these contaminated sites may require appropriate cleanup and restoration, which could cost billions of dollars and put tremendous pressure on our limited financial resources. Therefore, the development of a selective flotation process to separate such radionuclides from contaminated soils should be considered. In this study, both a pure depleted UO2 sample and three synthetic UO2/soil mixtures were used to evaluate surface chemistry features and to examine the possibility for the flotation of fine UO2 particles from selected soils. It was intended that this model system would be a reasonable representation of contaminated soils such as those found at the Nevada Test Site which are reported to be contaminated by PuO2 fallout. The effect of reagent schedule, particle size distribution, and surface charge are discussed with respect to the flotation separation of the UO2/soil mixtures. It was found that both commercial fatty acids and reagent grade sodium oleate are effective collectors for UO2 flotation provided the pH is adjusted to the range of pH 8-9. The bench-scale flotation results successfully demonstrated that froth flotation technology can be used to remove UO2 from such model contaminated soils with appropriate flotation chemistry conditions which depend on the soil characteristics and other pretreatment procedures. In the best case, 90.2% of the UO2 was removed from a UO2/NTS soil mixture (119 ppm UO2) and the soil reduced in UO2 contamination from 119 ppm to 17 ppm in a single stage bench flotation. The impact of clay slimes present in the soil is revealed by the results which show that, for example, for a deslimed soil (28x400 mesh and 100 mg UO2/kg soil) 85¬90% UO2 recovery can be obtained with a reduction in contamination to 4.6 mg U02/kg soil.

Jan 1, 1995

By K. Narayana Swamy

Experimental results of 3-phase mixing in a physical model of a CCRL for metals refining, at high levels of bottom gas injection (up to a superfIcial gas velocity (Us) of 12.5 cm/min), are presented. A thermal tracer technique was used to elucidate both longitudinal mixing and interphase heat transfer. The results indicate that even under conditions of significant bottom gas injection, it should be possible to maintain acceptably low longitudinal mixing (D. < 20 cm2/s and D/uL < 0.1) in the CCRL. Interphase mass-transfer coefficients of the order of 0.02 cm/s and higher, are predicted from the measured interphase heat transfer coefficients using the mass and heat transfer analogy. Adequate performance is likely to be possible for an industrial CCRL, based on extrapolation of these results to full-scale conditions.

Jan 1, 1996

By Yotamu Stephen Rainford Hara, Animesh Jha

The investigation focuses on a low temperature recovery of Cu and Co from a 40 wt% SiO2-(30 wt%Fe,6 wt%Al)2O3-10wt% CaO-7wt%CuO-7wt%CoO slag over a temperature range of 1173K to 1323K. The alloy phases containing Cu-Co and Fe-Co alloy formed via the carbothermic reduction of oxides: MO + C = M + CO(g), where M represents metallic copper, cobalt or iron. In the direct reduction of oxides, the recovery of metallic phase was well below 90% at 1323K, due to the kinetic barrier which was analysed and attributed to oxygen and metal-ion transport in the slag. This barrier was overcome by adding CaSO4 and carbon, which yields a matte (MS) phase via MO + CaSO4 + 4C = MS + CaO + 4CO reaction. Lime thus produced in situ participates in metal oxide/metal sulphide reduction reactions, which are analysed with the help of X-ray powder diffraction, scanning electron microscopy, and thermogravimetric analysis.

Jan 1, 2014

By C. Pereira

Spent nuclear fuel (SNF) can be treated in a molten salt electro refiner for conversion into metal and mineral waste fonns for geologic disposal. The fuel is dissolved in molten chloride salt. Non-transuranic fission products in the molten salt are ion-exchanged into zeolite A, which is subsequently mixed with glass and consolidated. Zeolite was found to be effective in removing fission product cations from the molten salt. Breakthrough of cesium and the alkaline earths occurred more rapidly than was observed for the rare earths. The effluent composition as a function of time is presented, as well as results for the distribution of fission products along the length of the column. Effects of temperature and salt flow rate are also discussed.

Jan 1, 1996

By H. Deveci

Bioleaching/biooxidation is essentially a dissolution process with the involvement of acidophilic bacteria acting as the "catalyst" to accelerate the dissolution of metals from sulfide minerals. The contribution of bacteria to the metal dissolution is closely controlled by the growth of bacteria, which is itself affected by the physico-chemical conditions within the bioleaching environment. There are a number of operating parameters controlling bioleaching processes, which are required to be maintained within a certain range in the leaching environment whereby the activity of bacteria with the resultant oxidation of sulfide minerals can be optimized. In this regard temperature, acidity, oxidizing conditions, availability of nutrients, oxygen and carbon dioxide, surface area and presence of toxic ions are of prime importance for control and optimization of bioleaching of sulfide ores/concentrates. Bioleaching processes are temperature and pH dependent with optimum metal dissolution occurring in a particular range where the bacterial strain is most active e.g. mesophiles at 35-40°C and pH 1.6-2.0. Provision of nutrient salts is required to maintain the optimnm growth and hence metal dissolution with the quantity of nutrients apparently being dependent on the availability of substrate i.e. head grade/pulp density of an ore/concentrate. Oxygen transfer is one of the most critical factors since the oxygen levels below 1-2 mgll may adversely affect the oxidizing activity of bacteria. Bioleaching rate tends to improve with increasing the surface area at low pulp densities but, in practice. the pulp density is limited to -20010 w/v. Increasing concentrations of ions such as cr may also adversely affect the oxidative activity of bacteria. Keywords: Bioleaching, Biooxidation, Acidophilic bacteria

Jan 1, 2003

By A. W. Bryson, K. C. Lenthall

"With the growth in the use of cobalt in industry, interest in its extraction and recovery has increased. With this increased interest comes the need for a fundamental knowledge of the processes involved in the recovery of cobalt metal. This paper examines the effects of cobalt concentration, catholyte pH, operating temperature and current density on cobalt electrowinning with respect to the current efficiency, cell potential and nature of the cobalt deposit. It is found that the cobalt concentration and catholyte pH affect the current efficiency, while current density and temperature affect the cell potential and thus the specific power consumption. Pitting on the deposit is affected by the catholyte pH and the operating temperature. Furthermore, the effect of feed flow-rate on catholyte pH, and thus current efficiency, is investigated. A model to predict the cell performance, which includes the flux of hydrogen ions through the diaphragm, is proposed.IntroductionCobalt metal is a silvery transitional metal found between nickel and iron on the periodic table. Due to its resistance to corrosion and other properties under high temperatures and its good work-hardening characteristics, it is favoured in alloys used in high temperature applications. These include aerospace, aircraft and high speed tools. Other applications include its use as a colourant in glass and ceramics, a drying agent in paints, a nutrient for livestock, a catalyst in the petroleum industry and, in the medical field, in prosthetics and radiology.The main deposits of cobalt are found in Central Africa, specifically Zaire and Zambia, although deposits also occur in Morocco, Canada and Australia. The cobalt is generally associated with other transitional metals including nickel, iron and copper. It is generally extracted by hydrometallurgical means and recovered from solution by electrowinning or hydrogen reduction. Little data [1-2] exists in literature on the electrowinning of cobalt from aqueous solutions. This paper investigates the effects of various operating conditions on the current efficiency, cell potential and deposit nature under continuous operation."

Jan 1, 1997

By Richard W. Lawrence

Leaching of copper from sulfide minerals using biooxidation offers a potential route for copper recovery. Oxidation of . sulfide sulfur can proceed either; to sulfate or to elemental sulfur depending on mineralogy and process conditions. The advances in commercial application of biooxidation for sulfidic gold ores has made available operating and cost data which allow the derivation of conceptual costs for copper ore processing for comparison with conventional processing routes. Although costs for copper biooxidation generally remain high relative to conventional smelting, application might be competitive in specific cases. Biooxidation becomes more competitive in the general case if the cost ofS02 emissions in pyrometallurgical processing were to be internalized to a greater degree than currently required. This paper describes the technical aspects of biological processing of copper sulfide ores and concentrates, specifically with respect to the fate of sulfur. The environmental and economic implications of the biooxidation route are discussed in relation to conventional processing.

Jan 1, 1996

By T. T. Chen

A mineralogical study of copper anodes and copper anode slimes was carried out to elucidate the silver phases present and the behaviour of silver during copper electrorefining. Most of the silver in the anodes is in metastable solid solution in the copper metal. As the copper dissolves, silver also dissolves, but is rapidly removed from solution by a variety of reactions. Some of the silver is precipitated as Ag by cuprous ions and some is precipitated as a complex CU-Ag-Pb-As-Se oxidate phase. Much of the silver, however, reacts with copper selenides to form, progressively, (CU,Ag) 2se, AgCuSe and Ag2se. The reaction commences at the periphery of the selenide grains and progresses inward; the result is commonly a silver-rich species on the outside of a silver-deficient core. Slimes collected periodically throughout the electrorefining cycle show a progressive silver enrichment of the selenides. Traces of Ag2Te also may be present, but the telluride seems to J:ie a rare constituent of most raw anode slimes.

Jan 1, 1989

By Maija-Leena Metsärinta

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. SEMIEDS 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 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