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By P. M. Prasad

The last two decades have witnessed the emergence of numerous hydrometallurgical and direct processing techniques for the extraction of some metals from pocketed/lean/complex sulfide ore deposits. A new approach with some inherent technological merits, investigated in recent years, is the lime-enhanced reduction of metal sulfides. Thermodynamic aspects relevant to the lime-enhanced reduction of metal sulfides by H2,C0 and C are discussed. A survey of the researches on the basic features of and factors influencing the lime-scavenged reduction of selected sulfides and sulfide concentrates reveals that lime tremendously enhances the sulfide reduction rates (up to 100 times) and drastically reduces the sulfur emission into off-gas to negligible levels. Further successful practice of lime-enhanced reduction requires only a moderate temperature of reduction (characteristic of each sul¬fide) and, in the case of gaseous reduction, relatively low gas flow rates. Relevant kinetic aspects of the concerned reactions that have a bearing on process development and its understanding are also briefly discussed. A conceptual scheme of general applicability for the processing of sulfide concentrates by the lime-enhanced reduction technique consists of three main steps: (0 lime-enhanced reduction by a suitable reagent (e,g., H,2, CO, gasified coal, water gas), (ii) separation of the product metal from the dry slag (CaS + unused CO) by mechanical separation, magnetic/gravity concentration or flotation and (iii) melting and refining by standard procedures. This novel approach, which is patently less complex, is expected to employ basically simpler flow sheets at comparatively lower operational temperatures and aid in pollution abatement. Potential for developing such a route for the small scale extraction of metals like copper, molybdenum and antimony is indicated. Possibility of utilizing this technique for the production of fibers/ filaments of some metals is also outlined.

Jan 1, 1983

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

By L. Petitnicolas

The experimental study of nitrogen absorption and its removal from a liquid Ni-20%Cr alloy at 1873 K has been undertaken, using an experimental, apparatus based on the Sieverts technique in order to determine the solubility of nitrogen in the alloy. as well as the kinetics of nitrogen transfer across the gas/melt interface. Experiments show that nitrogen solute equilibrium content can be calculated using the Sievens law. Measurements point out the nitrogen absorption reaction rate to be well described by first order kinetics, whereas experiments on nitrogen removal reveal that the rate is better expressed using a second order equation.

Jan 1, 1996

By Demaerel. J. P.

Arsenic plays a major role during electroreflning of copper. Both the arsenic content in the anode and the arsenic concentration of the electrolyte have, in conjunction with other impurities such as lead, antimony, bismuth and oxygen, a direct influence on the quality of the cathode. The mechanisms are currently slime. inclusion and precipitation of insoluble compounds in the bulk of the electrolyte. Arsenic has also been reported to have a depassivating effect on the anode. An influence on the anode slime adhesion has also been found. A literature survey is given and these data are compared with and completed by our own results based on lab and pilot scale experiments as well as on Olen tank.house practice.

Jan 1, 1987

By Garry W. Warren

The brass foundry industry produces a significant amount of waste sand containing Cu, Zn and Pb which is often classified as a hazardous waste due to Pb content. The potential application of a hydrometallurgical process to treat the sand by extracting metal values and thus detoxifying the material has been investigated. The process involves leaching of metal values followed by cementation. The emphasis of this investigation was on the leaching step, although some preliminary cementation experiments have been performed. In order for any alternative treatment scheme to be successful, the smaller size fractions of the sand must be addressed. Experiments have been performed on five individual size fractions using various lixiviants HCI, acetic acid and HCI/NaCI. Cu extraction was found to be slower than either Zn or Pb. Results obtained in this investigation indicate that copper is present in two forms, an oxide form which dissolves rapidly and is insensitive to the level of oxygen, and a less soluble form, probably metallic which dissolves more slowly and requires an oxidizing agent. The presence or absence of oxygen had no influence on the rate of Zn dissolution indicating that zinc is present mostly in oxide form. Toxicity Characteristic Leaching Procedure (TCLP) tests showed that residues could be produced which meet the toxicity limit for lead. Preliminary cementation experiments have also demonstrated the feasibility of Cu and Pb recovery.

Jan 1, 1991

By G. D. Sandrock

The science and technology of roan temperature rechargeable metal hydrides began about 1969 with the discoveries that the intermetallic Compounds LaNi5 and TiFe could be, conveniently hydrided and dehydrided at roan temperature and modest H2 pressures. Subsequently, this lead to the development of a broad family of REE-containing AB5 hydrides and numerous applications that make use of the extraordinary H2-absorption and reaction-heat properties of these materials. Some of the applications include H2 storage, compression and separation, as well as heat pumping, heat to mechanical energy conversion and electric energy storage. This paper briefly reviews the fundamental phenomenology of metal hydrides, the history of the use of REE's in rechargeable metal hydrides, the practical engineering properties of these materials and the applications that have evolved around them. The rechargeable nickel metal hydride battery, a new vial alternative to NiCd cells, stands at the forefront of the applications.

Jan 1, 1992

By Xun An

Slag from an electric slag cleaning furnace was injected with methane and air mixtures to facilitate the recovery of copper and cobalt. The effects of methane-to-air ratio, gas flow rate and temperature on the reduction and metal separation were investigated. The results showed that over 90 percent copper and up to 60 percent cobalt could be recovered from the slag with a gas utilisation of around 70 percent, as calculated by thermodynamic simulation. Methane-to- air ratio was a major factor affecting the rate of reduction under the present experimental conditions. Further, injection of gaseous reductants greatly enhanced the coalescence and settling of entrained metal droplets. A reduction mechanism is proposed and the factors influencing the coalescence of copper droplets are discussed.

Jan 1, 1998

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By F. T. Principe

In order for solvent extraction technology to be acceptable as an alternative to existing jarosite precipitation circuits, iron must be cleanly separated and concentrated into a feed stream suitable for downstream iron by-product recovery which meets market specifications and economics. Ten years ago, significant progress was made in a joint McCill University/CANMET project that involved iron extraction with mono(2-ethylhexyl) phosphoric acid and stripping with HCI. Our iron solvent extraction research was reactivated recently by looking into this and other members of the organophosphorus extractant family. Our research focuses on the mechanisms and control of anion (SO42/CI) transport across the various phases (Rafinate/Organic/Strip), iron build-up in the strip liquor, and extractant stability/selectivity. In this paper, these issues along with some other performance parameters are discussed using data derived from an extensive search of the two commercially available and best known members of the organophosphorus family, di-2-ethylhexyl (D2EHPA) and mono-2-ethylhexyl (M2EHPA) phosphoric acid. Further in this discussion, the challenges lying ahead in the development of sx systems that overcome the deficiencies of D2EHPA and M2EHPA are outlined. In particular, the necessity of considering secondary separation technologies that can further concentrate iron values in the chloride strip liquor to levels economically attractive for the production of saleable iron oxide by pyrohydrolysis is addressed.

Jan 1, 1998

By J. W. Perez

A simple exponential model has been developed (Perez and Aplan. Process Mineralogy, VI, 1986) to describe the fractional yield of a given species out of a locked assemblage: Fractional Yield of Species A = a e X/U where 'X' is particle size and 'a' and 'U' are constants. In the present study, the general validity of this model has been further demonstrated. experimentally, for the liberation of coal and pyrite out of various raw coals and beneficiated fractions using a variety of crushing devices. Using data from the literature, the model is also shown to be applicable to the liberation of sulfide minerals out of ores.

Jan 1, 1987

By Jennifer Murphy, Brad S. Schake, Karol Holmes, John R. FitzPatrick, Mike H. West

"The separation and purification of uranium from either nitric acid or hydrochloric acid media can be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps.We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (1 DO-gram) flow experiments, using depleted uranium, were done after the small-scale evaluation of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos.Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process.Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail."

Jan 1, 1996

By Walter Curlook

An atmospheric acid leaching process for leaching nickel and cobalt from highly-serpentinized saprolitic fractions of nickel laterite deposits has been developed and patented [I]. The process involves leaching the highly-serpentinized saprolitic portion of the nickel laterite ore profile in strong sulphuric acid solutions at atmospheric pressure and temperatures between 80°C and 100°C, essentially autogenously, to extract over 85% of its contained nickel content and a large proportion of its cobalt content after leaching times of about one hour. The amount of sulphuric acid used in the leaching process is between 80% and 100% by weight of the finely ground highly-serpentinized saprolite ore on a dry weight basis. The metal values are recovered as intermediate products. Key words: Atmospheric Leaching; Nickel Oxide Ores; Laterites

Jan 1, 2004

By I. Gaballah

The electrochemical behavior of a chalcopyrite concentrate having a high pyrite content was studied in HC1 by potentiodynamic, potentiostatic and galvanostatic experiments using a cell having separate anodic and cathodic compartments. Anodic oxidation of chalcopyrite particles was realized both by their contact with the cunent feeder and by reaction with ferric and cupric ions. An increase of current leads to a more selective dissolution of chalcopyrite. Surface passivation was observed after an electrolysis time related to the cell current. Cathodic reduction of chalcopyrite concentrate seems to be more promising. Almost complete conversion of chalcopyrite to a copper sulfide (Cui.8.S) is observed, whereas no reaction of the pyrite was detected. This confirms the possible selective dissolution of copper from the chalcopyrite concentrate. Copper sulfide obtained by cathodic reduction was leached using a cupric chloride solution.

Jan 1, 1994

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and l200°C, positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation where negative deviations were observed.

Jan 1, 2003

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By H. C. Roland Kammel

Stannous sulfate electrolytes are widely used nowadays in electrolytic tin production. Characteristic features of this electrolysis process are that dense cathode deposits can only be obtained by additions of organic additives and that so called ?black mud is formed on the anode surface which leads to an increase in cell-voltage. In order to prevent excessive cell-voltages or oxygen evolution the black mud has to be removed periodically. Studies in laboratory scale have been performed about the effect of different organic additives on electrolytic tin deposition and the formation of surface layers on pure and industrial tin anodes. Results reveal that organic addition agents are effective in reducing cathode roughening as well as extending the covering time of the anode ?by black muds.

Jan 1, 1985

By Batric Pesic

Dissolution of gold with elemental bromine was studied by using a rotating disc technique. The main parameters studied were: bromine concentration, stirring speed, pH, and temperature. Additionally, effect of copper, iron, and manganese was also examined. A special attention was paid to elucidate the role of cations, primarily Na+, during gold dissolution. It was found that gold dissolution with bromine was characterized with two pH regions. Below pH=7, gold dissolution was independent of pH, and above this value, gold dissolution decreased with pH increase. Gold dissolution rates were proportional with concentration of bromine. Two regions, diffusional and kinetic, were observed with respect to stirring speed. with respect to the role of Na+, and cations in general, they play absolutely no role during gold dissolution with bromine, unless they are in their lower oxidation state and become oxidized by bromine. In that case they have a negative effect because of bromine consumption.

Jan 1, 1991

By D. M. Hausen

A refractory siliceous low-grade silver ore (265 g/t Ag) from a prospect in Sonora, Mexico was investigated mineralogically and metallurgically to evaluate extraction of the silver by conventional methods. Approximately half of the silver was recoverable, occurring as coarsely crystalline acanthite (70-300 Am) that was liberated in material crushed to minus 10 mesh. The remaining silver is refractory and occurs mostly as finely locked (-2 to 0.2 Am) acanthite in cherty quartz, and as minor amounts of finely disseminated stylotypite or freibergite in fluorite. The mineralogic data have thus served to explain the 50-60% recovery of silver by flotation and cyanidation.

Jan 1, 1991

By John R. FitzPatrick

The separation and purification of uranium from either nitric acid or hydrochloric acid media tan be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated' to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps. We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (100-gram) flow experiments using depleted uranium, were done after the small-scale evaluation Of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments' involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and' amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process. Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail.

Jan 1, 1996

By Du Sichen, S. Seetharaman, A. Jakobsson

"In the Present paper, the principles of oxygen potential measurements have been discussed along with the design details for oxygen sensors that are used in copper industry. A description of some of commercial probes is presented along with their salient features. The application of these sensors in flash smelting, converter and casting sections of copper production are discussed along with their implications on process optimization.I. IntroductionThe high temperature galvanic cells have come into prominence on account of their numerous applications in both fundamental as well as applied measurements. Since the inception of the oxygen-ion conducting electrolytes like ZrOrCaO·by Kiukkola and Wagner [1], the oxygen concentration cells have been extensively used in laboratories as well as in industries. In metal-production technology, these cells have been used to monitor the oxygen potentials in metallic, slag as well as gas phases and also to control and styr metallurgical processes. The pioneer among the various industrial users of such cells is the copper industry. To-day, high temperature solid electrolyte cells involving oxygen ion conducting electrolytes have become an integral part of copper pyro-refining and continuous casting. In the present paper some of the applications according to the industrial processes are described including the developments that are going on in the European scene."

Jan 1, 1997