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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 Chang-Dong Li

Cadmium ingot and nickel powder were prepared by high-temperature distillation, solvent extraction and liquid phase reducing method with spent Cd-Ni batteries as raw material. The impacts of the temperature in the distilling stage, the concentration of H2SO4 in the leaching stage, the pH value in the extracting stage and the dosage of hydrazine in the reducing stage were discussed respectively. The as- prepared samples were characterized by the means of X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic absorption spectrometry (AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). The results showed that the recovering efficiencies of Cd and Ni reach 99.5% and 99.3%, and the purities of Cd ingot and nickel powder were higher than 99.90% and 99.80%, respectively.

Jan 1, 2009

By Andrew Wessman

Keywords: Recycling, Electrodeposition, Recovery, Dilute, Dissolved Metal Ions In order to facilitate the recovery of pure metals from solutions containing a mixture of dissolved metal ions, a pulsed electrodeposition method was developed. Using this method, it is possible to selectively remove metal ions from solution based upon the electrochemical potential of the particular ion desired. The use of pulsed electrodeposition rather than direct current electrodeposition creates an electrodeposited material with better morphology, increases electrical efficiency of the process, and avoids problems with short circuiting between electrodes. Using this method, it is possible to recover dissolved metal ions in a purified form in one simple step, and therefore maximizes recovery of the metal ions while obtaining them in a saleable form. This method is likely to be useful in improving the recycling process for numerous complex metal mixtures and alloys.

Jan 1, 2005

By María Eugenia Castro, Silvia Galasso, Jorge Duca, Claudia Osuna, Ernesto Esparza

"We present a procedure for treatment of non-active solutions equivalent to the solutions obtained from dissolution of ionic exchange resins used in purification of a nuclear reactor primary cooling system containing Co, Ni, Cs and its isotropic varieties as main radioactivity source. Finally it is immobilized into a ferritic matrix by calcination which avoids its future leaching into environment.In order to achieve the objective of this treatment, a bivalent and a trivalent iron salt is added to the solution. Then, either a base or an acid is added, depending on the initial pH of the treated solution, with a Cs precipitating additive in order to reduce Co and Cs by precipitation, flocculation and adsorption. Controlling the amount of precipitating reactives it is possible to modify the activity/volume rate becoming a medium into a low radioactivity waste.The leaching test result applied over the ferritic sample is lower than the minimum limit established by law. Therefore, it can be kept safely in a interim storage."

Jan 1, 2008

By Hirokazu Narita

Keywords: solvent extraction, precious metals, thiodiglycolamide, rapid separation, hydrochloric acid The solvent extraction of some precious metals (Pd(II), Pt(IV), Rh(III) and Au(III)) and base metals (Fe(III), Cu(II) and Zn(II)) in a hydrochloric acid solution was carried out using N,N'-dimethyl-N,N'-dioctyl-thiodiglycolamide (MOTDA) dissolved in the mixed solution of 80 vol-% dodecane and 20 vol-% 2-ethylhexanol. The extraction percentages of Pd(II) and Au(III) in the 0.01 M MOTDA-1.0 M HCl solution system are 99.6% and 71.8%, respectively. In contrast, the other metal ions are hardly extracted under the studied conditions. The Au(III) and Pd(II) extracted in the organic phase are easily back-extracted with a 1.0 M thiourea/1.0 M HCl solution. A comparison with the conventional extractant for the Pd(II) separation, di-n-hexyl sulfide (DHS), revealed that the extraction rate of Pd(II) with MOTDA is much greater than that with DHS. The extraction percentage reached over 99% in less than a 2 min contact time. However, in the DHS-Pd(II) system, it takes about 240 min to achieve the extraction equilibrium. Furthermore, MOTDA can quantitatively extract Pd(II) up to half the molar amount of MOTDA. Therefore, MOTDA is a promising extractant for Pd(II) from the HCl solution after the removal of Au(III).

Jan 1, 2005

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 Emma Arakelova

An increase in concentration of a Zn-containing volatile complex for synthesis of ZnO films was investigated when processing their target by ultraviolet radiation emitted by mercury lamp. The experiments were carried out using a flow-type quartz reactor. ZnO tableted target was preliminarily irradiated during 2 to 7 hours. H2O2 (98%) vapor at 25Pa passed through the reactor with ZnO target at 373K. As substrate material, five subsequent quartz cylinders were used at 423K. The experiment lasts 4 hours. H2O2 decomposition on ZnO surface was accompanied by formation of a Zn-containing volatile complex which passed in gas phase and decomposed on the substrates with isolation of final ZnO. The concentration of the Zn-containing volatile complex (N) in gas phase increases with UV pre-irradiation time (t) (without irradiation N = 1.05 1011 particles/cm3; after t=2 hours, N = 5.19 1011 particles/cm3, after t=4 hours, N = 9.95 1011 particles/cm3; after t=7 hours, N = 1.86 1012 particles/cm3.

Jan 1, 2006

By Jacques J. Eksteen

Metallurgical accounting around toll treatment smelters pose a number of challenges. This paper reviews the requirements for good sampling practice, and how conflicting requirements for good furnace operation and design often makes reliable closure of the metallurgical balance tenuous at best. Typical physical causes of variance and bias will be identified. The propagation of error (in the form of variance) will be discussed for a copper smelter.

Jan 1, 2006

By Pinai Mungsantisuk

Keywords: Pd-Ni alloys, Pd-Fe alloys, Pd-Co alloys, Magnetostriction, Magnetic Properties The presence of congruent melting minima, the occurrence of ferromagnetic transition over a large composition range, and FCC type crystal structure make Pd-Ni, Pd-Co, and Pd-Fe based systems attractive candidates in our search for materials with no rare-earths, large low-field magnetostriction, and good mechanical properties. The presence of paramagnetic-ferromagnetic transition over a broad range of composition also provides opportunity for fundamental studies. In this work, we have examined the magnetic and magnetostrictive behavior of Pd-Ni, Pd-Co, and Pd-Fe alloys over the entire composition range. Alloy sample rods were prepared by arc melting and casting. X-ray diffractometer was used to obtain lattice parameter data. Magnetostriction was measured along the rod axis using strain gages. Magnetic properties were measured using a vibrating sample magnetometer.

Jan 1, 2005

By Toshiyuki Kawai

Copper concentrate smelting directly in P-S converters was started at Onahama Smelter in 1983. Thereafter, the tonnage of concentrate smelted through the P-S converters increased, such that by 2002, it equaled the tonnage smelted through the reverberatory furnaces. In 2003, 56% of the total copper concentrates treated at Onahama Smelter were processed directly through the P-S converters. Technical improvements are reviewed and advantages of direct smelting in P-S converters are reported.

Jan 1, 2005

By J. C. Huyhua

The effect or various oxidants on gold and silver dissolution in thiourea solutions (0.05 M in H2SO4) was studied using the rotating disc technique, a.t 2s c and 600 rpm. These studies were carried out at constant (4:1) initial molar ratio or thiourea to oxidant concentrations, to produce 50 % thiourea. oxidation. The initial dissolution rate of gold was approximately four times higher in the presence. of ferric sulfate (5.37 x 10-3mg cm-2 s-1) than in the presence of hydrogen peroxide (H2O2), potassium persultate (K2S2O3), or monopersulfa.te (KHS06). The dissolution rates for silver were considerably lower than gold for the same oxidants. Oxidation of thiourea in the presence of peroxygen and persulta.te compounds is a. fast reaction and it is completed in less than ten minutes. On the other hand, the oxidation or thiourea with? ferric.sulfate is slow, yielding a second-order reaction rate constant k = 6.09 I mol-1 h-1. Sulfur formation in the ferric thiourea system begins when ferric ion reduction approaches to completion. With hydrogen peroxide, sulfur is observed at lower thiourea concentration than ferric. Suifate. The presence of a large excess or free thiourea i.e., s to 20 % thiourea oxidation) retards sulfur formation and maintains favorable dissolution rates. Finally, carbon-in-leach experiments indicate that thiourea solutions a.re stable for several days, with ferric sulfate or hydrogen peroxide. The dissolution rates of gold and silver doubles in the presence or activated carbon when hydrogen peroxide is used as oxidant.

Jan 1, 1989

By Anat Deepatana

Bioleaching of nickel laterite ores is the extraction technology based on the use of heterotrophic micro-organisms and their organic acid products to dissolve metals from oxide minerals. This study examined the chemical leaching kinetics of limonite and nontronite ores with metabolites including citric, lactic and malic acids. The leaching process was found to follow the chemically controlled model. The leaching kinetics was found to be significantly influenced by the acid strength or dissociation of acids in solution. Although increasing the acid strength increased the rates of leaching, this trend was not indefinite. An optimal acid concentration that defined the fastest leaching rates was identified for each acid. The amenabilities of the minerals hosting the nickel and cobalt in limonite and nontronite to organic acid leaching were also established.

Jan 1, 2006

By Wenshan Zhang

Three important methods of removing Fe in hydrometallurgy of zinc, manganese, copper, nickel, cobalt and etc are described, including neutralized hydrolysis method, jarosite method and goethite method. The reactions, technical requirements and thermodynamic analysis during Fe removal process are also discussed in this paper.

Jan 1, 2006

By Kim Fagerlund

Boliden Harjavalta Oy operates a copper smelter in Finland, which is based on flash smelting together with Peirce-Smith converting of copper matte. This paper reviews a case study when a high arsenic feed mixture was successfully eliminated in order to guarantee the anode quality. Based on theoretical and practical knowledge in slag chemistry at Outokumpu Research, the CaO-fluxing practice was introduced. Description of a thermodynamic simulation using MTDATA and implementation of the results into converting practice is given. Results showed that the impurity fluctuations in raw materials could be effectively controlled by efficient utilization of different slag chemistry.

Jan 1, 2005

By Andrey V. Tarasov

To carry out a physicochemical substantiation of a transition to ?soft? modes of reduction of calcine obtained by desulfurizing roasting of nickel concentrate produced as a result of copper-nickel converter matte separation in a nickel anode production circuit, an analysis has been conducted of the macrokinetic behavior of actual calcine samples in the presence of gaseous H2-CO mixtures and solid reductant additives. Within a temperature range of 900°C to 1100°C the main regularities typical of the calcine reduction process with individual gases (H2, CO) also take place when using a gaseous mixture. Under the conditions of low-temperature (900°C to 1000°C) nickel oxide reduction with products of fuel oil conversion in the presence of coke, the role of the latter is insignificant from the technological viewpoint. As a result of the present investigations, we have obtained analytical expressions of macrokinetic parameters of the reaction interaction within the [NiO] calcine-H2-CO-C-CO2-H2O-O2-N2 system.

Jan 1, 2005

By Pengfu Tan

Converter slag chemistry control has played an important role in optimizing converter operations. A thermodynamic model of copper P-S converter has been developed to predict the behavior of magnetite in the converter slag. Predictions of bath temperature, slag and matte compositions, and magnetite content in the slag have been validated by industrial data. The effects of fluxing strategy, returns and skim charges, oxygen enrichment, and temperature on the magnetite formation in the slag have been predicted and discussed. Some improvements of the industrial operations have been presented.

Jan 1, 2005

By M Kolbe

Co-Cu exhibits a metastable miscibility gap in the region of the undercooled melt. Specimens have been undercooled and solidified containerlessly into the metastable miscibility gap in an electromagnetic levitation facility (EML) and in drop tube (DT) experiments. Due to the high undercooling the velocity of the solidification front is very high and the microstructure is frozen in instantaneously. The microstructure of samples processed in the EML is influenced by the electromagnetic stirring due to the induction of electrical currents into the melt. A variety of microstructures has been observed. After undercooling below the binodal the liquid melt separates into the Co-rich L1-phase and the Cu-rich L2-phase. Two basic morphologies of the L1-phase can be observed, they can be attributed to the transition in dendrite growth from diffusionally and thermally controlled to only thermally controlled growth. Transient microstructures are observed after solidification in the vicinity of the binodal. Drop tube experiments, which lead to a rapid solidification of a distribution of droplets under reduced gravity conditions, in contrary allow for the observation of the early stages of demixing: the microstructure shows a homogeneous distribution of spherical particles of the minority phase in the droplets. The cooling rate of the droplets and its dependence on the droplet radius has been calculated. The solidification velocity as a function of undercooling has been measured in the EML for the composition Co-lB.Bat%Cu. The data are analysed in the framework of the LKTlBCT model with a velocity-dependent distribution coefficient as well as within a model of Galenko and Danilov using a kinetic growth coefficient of u=0.22 m/Ks.

Jan 1, 2002

By Scott A. Shuey

Keywords: E-Waste, Pyrometallurgy Many might think addressing the issue of e-waste is a new area of study. Electronics disposal has been discussed in some circles for at least the past 25 years. The recycling of electronic waste (e-waste) tends to be a rather complex undertaking when considering the intimate bonding of materials in the average printed circuit board. The development of a recycling process is further complicated when considering the wide variety of products being generated under the heading of ?electronics.? Focusing only on the primary constituents (polymers, Cu, Al, Fe, etc.) tends to lead one to fairly simple flowsheets. Ignoring trace elements, and the various halide species generated, will lead process engineers down a development path that is sure to cause material handling issues. Researchers at Colorado School of Mines are modeling the complex chemistry that exists within the body of e-waste?comprising 39 of the known elements. An understanding of the systems thermodynamic behavior will result in the development of a more robust, long-term process for the recovery of valuable materials from the e-waste stream.

Jan 1, 2005

By Melissa L. Trapani

Keywords: Copper, Taphole, Flow Instability. ?Blister spitting? is a flow irregularity where the molten blister copper stream ? or part thereof ? sprays from the taphole exit rather than following a regular flow profile to the collection box. As well as being a general ?housekeeping? issue, the unpredictable nature of the flow is a threat to operator safety. Also, the aggressive flow pattern may contribute to the mechanical wear of the taphole refractory, compromising the integrity of the taphole. This paper brings together a collection of first-hand observations and reports from process personnel, and suggests some theories as to the causes of blister spitting.

Jan 1, 2005

By Ji-He Wei

Keywords: stainless steel, AOD refining, side and top combined blowing, mixing characteristics, water modeling The fluid mixing characteristics in the bath during the side and top combined blowing AOD (argon-oxygen decarburization) refining process of stainless steel have preliminarily been investigated on a water model unit of a 120 t AOD converter. The geometric similarity ratio between the model and its prototype (including the side tuyeres and the top lances) was 1:4. On the basis of the theoretical calculations for the parameters of the gas streams in the side tuyeres and the top lances, the gas blowing rates used for the model have more reasonably been determined. The influence of the tuyere number and position arrangement, and the gas flow rates for side and top blowing on the characteristics has been examined. The results demonstrated that the liquid in the bath underwent vigorous circulatory motion during gas blowing, without obvious dead zone in the bath, resulting in a well mixing effectiveness. The gas flow rate of the main tuyere had a governing role on the characteristics, a suitable increase in the gas flow rate of the subtuyere could improve mixing efficiency, and the gas jet from top lance could make the mixing time prolong. Corresponding to the oxygen top blowing rate specified by the technology, a roughly equivalent and good mixing effectiveness could be reached by using six side tuyeres with an angle of 27 degrees between each tuyere, and five side tuyeres with an angular separation of 22.5 or 27 degrees between each tuyere. The relationships of the mixing time with the gas blowing rates of main-tuyeres and sub-tuyeres and top lance, the angle between each tuyere, and the tuyere number have been obtained.

Jan 1, 2005