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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 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

By Katsuyoshi Kondoh

The synthesis processing of Mg2Si or Mg2SiIMgO at lower temperature from the elemental magnesium alloy powder/chips and Si or SiO2 powder mixture was established via the repeated plastic working (RPW) based on Powder Metallurgy (PIM) process. RPW is much effective on the mechanical breakage of MgO surface films, which prevent from the solid-state reaction between Mg and Si powder. The solid-state synthesized Mg2Si particle of 200nm-2um is extremely fine, compared to that via the conventional casting process, causing the coarse one of 50-100um. This is because of not coarsening during the solid-state synthesis of Mg2Si. By using in-situ fonning process of Mg2Si via RPW and pre-heating before hot working such as extrusion and forging, the magnesium composite material with Mg2Si or Mg2Si/MgO dispersions was developed in employing Si or SiO2 particles, respectively. For example, when employing AZ31 chips as raw materials of the matrix, it has low density of 1.85g/cm3 and extremely superior mechanical properties, such as tensile strength over 350MPa with 5-10% elongation and Young's modulus of 47-50GPa, to the conventional Mg-Al-Zn alloys. The Mg composite alloy wires and pipes were produced via the hot extrusion process in the manufacturing plant, and also showed excellent mechanical properties.

Jan 1, 2003

By Serdar Aksu, Fiona M. Doyle

"CMP will be an essential process in the production of integrated circuits containing copper interconnects. This study aims to improve our mechanistic understanding of the role that organic chelating agents might play in the reactive slurries used in copper CMP. Copper dissolution behavior in EDTA arid glycine was first examined by producing potential-pH diagrams for the copper-water-EDTA and copper-water-glycine 'systems. The results of potentiodynamic polarization experiments were then considered in light of these diagrams. . In-situ polarization experiments were conducted to gain insight into the electrochemistry of copper during dynamic polishing in slurries prepared from EDT A and glycine.IntroductionCopper has recently started to replace aluminum as the interconnect metal in integrated circuits. Copper interconnection offers faster and more reliable integrated circuits due to its higher electrical conductivity and superior electromigration resistance (1). The damascene method is used to form multilevel interconnects in the manufacture of integrated circuit devices with copper metallization (2, 3). Copper is deposited by CVD or electroplating into vias and trenches etched in the interlayer dielectric (IDL), over a diffusion barrier usually made from titanium, tantalum or their nitrides. Chemical mechanical planarization (CMP) then prepares the wafer for the next deposition step, by removing excess copper and planarizing the surface. During CMP, the wafer is rotated and pressed against a rotating platen covered with a polishing pad. Chemically active slurries containing submicron size abrasive particles (Si02, Al20 3, ceria, diamond, etc.) are applied. Both the mechanical action of the abrasive particles and the chemical action of slurry constituents remove material from the wafer surface. Planarization results because material is removed faster from protruding regions on the surface than from recessed regions. Since CMP can globally planarize .the entire wafer, it has become one of the key technologies for producing integrated circuits with copper metallization."

Jan 1, 2000

By N. Kanari

One of the criteria to define the market value of chromite concentrate is its chromium to iron ratio. Changing this ratio for a definite chromite mineral is impossible by physical processing. This study investigated the possibility of increasing this ratio through the carbochlorination and the oxychlorination of chromite concentrates. Experiments are carried out up to 1000 °C. The characteristics of samples and reaction products are determined by SEM, XRD and chemical analysis. The carbochlorination of a chromite concentrate at about 600 °C leads to the . selective partial elimination of iron allowing a higher Cr/Fe ratio of the treated concentrate. Selective extraction of iron could also be achieved at about 950 °C by oxychlorination. In this case, a part of chromium contained in the concentrate is recovered as chromium oxychloride. The obtained residue had high content of Cr, Mg and A1 oxides. Such material has probably better chemical and thermal properties that may. be useful for foundary and refractory applications. Two flow-sheets for the beneficiation of the chromite concentrates using carho- and oxychlorination are suggested.

Jan 1, 1997

By James C. Barker

Recent investigations of a 55-km long trend of intrusive complexes on southern Prince of Wales Island have identified significant resources of Nb, Y, REE. U, Zr, and a host of potential by-product metals. The northwesterly trend comprises multi-phased sodic alkaline and peralkaline diorite, monzonite, syenite, and riebeckite granite. There are at least three significant deposit types recognized, two of which, 1) pegmatite dikes/vein-dikes that zone laterally from the intrusions and 2) concentrically zoned pegmatites, contain most of the lithophile metals. A third, epigenetic replacement-type mineralization, contains much of the U resource. Other deposit types with minor or unknown resource potential include diatremes, carbonatite, and placers. This report summarizes the deposit evaluations, characterizes the mineralization, and estimates the resources. To date a total of 40.7 million tons of mineralized material is estimated as indicated or inferred. Most of the Y203 plus REO is at a grade exceeding 0.5% and half of the Nb20S exceeds 0.125%. Tonnage estimates would likely be substantially lncreased with additional exploration. Mineralogy is generally fine-grained and complex, and consists of more than a dozen principal REE-Y-Nb-U-Th-Zr phases, the sum of which may compose up to half of the rock. Approximately half of the REE-Y content comprises the heavy yttrium subgroup which is uncommon compared to deposits elsewhere. Although the Alaskan deposits are likely subeconomic at today's metal prices and consumption levels. recent technological advances suggest future demand may increase.

Jan 1, 1988

By Suguru Kohno, Yoshihiro Momose, Masakazu Honma, Tokirou Kamosawa

Copper metal surfaces have been examined by an extremely sensitive surface analysis technique called temperature programmed photoelectron emission (TPPE). The surfaces were ultrasonically cleaned and subsequently abraded by a screw in organic solvents and water. The TPPE apparatus is composed of a Geiger counter with Q gas (He+ iso-C4H10). The curve of photoelectron emission (PE) intensity vs. wavelength from 300 to 170 nm, termed PE spectrum, was repeatedly measured at different temperatures in the temperature- increase process from 25 to 350°C. The number of emitted electrons in a PE spectrum (PE total count) increased, reached a maximum at-250°C, and decreased with increasing temperature. With the surfaces cleaned alone in the liquids the maximum PE total count decreased in the order C3H70H > (CH3) 2CHOH > C2HpH > CHPH > H2O. With the mechanically abraded surfaces in the liquids the maximum PE total count changed as a function of the abrasion period and the maximum tended to appear at higher temperature with increasing abrasion period; the maximum value at 10-min abrasion decreased in the order H2O > CHpH > C2HPH > (CH3) 2CHOH > n-C3HpH. It was suggested that the TPPE behavior can be related to the acid-base interaction between the alcohols and the abraded metal surfaces and the presence of a contaminant over layer on the surface. From the XPS analysis of the 01 s spectra it was suggested that the chemical change of the adsorbed oxygen to oxide oxygen with temperature plays a substantial role in the appearance of the maximum PE total count.

Jan 1, 2000

By Youngkook Lee

The precipitation kinetics of NbC in ferrite matrix of the Nb microalloyed steel was investigated experimentally and numerically. The mole fractions of NbC precipitates formed at different isothermal temperatures were measured as a function of holding time by electrical resistivity test and were compared with both a mathematical model based on time-dependent nucleation and growth rates and the hardness. There is a good match among the calculated and measured precipitation kinetics of NbC and the hardness. The isothermal precipitation-temperature-time diagram of NbC in ferrite matrix of the Nb microalloyed steel was newly generated. Keywords: Precipitation, Carbide, Ferrite, Nucleation, Growth, etc

Jan 1, 2003

By G. B. Harris

Jaguar Nickel Inc. is developing the Sechol Nickel-Cobalt Laterite Project in Guatemala, Central America. Recognizing the potential advantages offered by chloride brine chemistry, Jaguar, at the facilities of Process Research ORTECH Inc, Mississauga, has developed an Atmospheric Chloride Leaching Process using a mixed chloride lixiviant to recover the nickel and cobalt, whilst leaving the majority of the iron and magnesium in the leach residue. Subsequent solution purification and mixed nickel/cobalt hydroxide product recovery is by standard precipitation methods, using recycled caustic magnesia, with a final stage of pyrohydrolysis of a portion of the concentrated magnesium chloride brine for recycling both the caustic magnesia and chloride lixiviant. The flowsheet that has been developed also offers opportunities for by-product recovery and efficient, environmentally clean process effluent management. The paper discusses some of the early leaching results in the context of strong chloride brine chemistry, with emphasis on how the controlling of water activity, hydrogen ion activity and chloride concentration permits the selective leaching of nickel and cobalt from an iron-magnesium matrix. Keywords: nickel, cobalt, iron, magnesium, Sechol, Guatemala, chloride, pyrohydrolysis

Jan 1, 2004

By William Petruk

The mineralogy of the primary and oxidized ores from the Malanjkhand porphyry copper deposit in India was studied to determine ore characteristics that affect metallurgy, and to assess applicable processes for recovering the copper. Three mineral assemblages were found. One occurs in primary ore, another in moderately oxidized ore, and a thir:d in intensely oxidized ore. Chalcopyrite, the main mineral in the primary ore, is relatively coarse-grained, with grain size increasing as the ore grade increases. High chalcopyrite liberations should be achieved at a relatively coarse grind, and good chalcopyrite recoveries should be obtained. The chalcopyrite, however, tarnishes readily and oXidizes to chalcocite in a relatively short time (several months). The presence of both the tarnished chalcopyrite and chalcocite may affect chalcopyrite flotation and reduce copper recoveries, The moderately oxidized ore occurs in an oxidized cap immediately above the primary ore, and stockpiled primary ore alters quickly to a moderately oxidized ore. Chalcocite is a major copper-bearing mineral in moderately OXidized ore. The concentrator processing this ore should be capable of handling a chalcocite-rich ore. The intensely OXidized ore contains a wide variety of acid-soluble copper-bearing minerals. Leaching may be required to recover the copper from them.

Jan 1, 1987