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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 H. A. F. de Souza, Dana S. Mills, P. E. Burgener

"ICP-MS has moved from a laboratory curiosity to a functional analytical tool. This paper discusses how ICP-MS has been used to solve difficult analytical problems encountered when analyzing various mine materials. Comparisons between analytical techniques applied to the analysis of gold and the platinum group metals illustrate the advantages and problems of ICPMS when. applied to trace levels of some metals iri the presence of ore grade metals. Interferences and matrix effects are compared to ICP, AA and Neutron Activation. The necessity to select chemical extractions which are compatible with ICP-MS are also discussed.The ICP-MS techniques explained in the examples on Au and precious group elements (PGE) have validity in analytical problems encountered in testing of trace metals in the presence of major elements found in mine materials. Exploration and environmental testing are other areas that require the same analytical approach to quantify trace levels in the presence of major interfering elements normally associated with mining environments."

Jan 1, 1999

Primary sulphidic gold ores in the Archean provinces of Western Australia can be broadly sub-divided into pyritic, pyrite-telluride, arsenical and antimonial types. Pyritic ores contain only native gold, and are essentially not refractory. Arsenical ores almost always carry some invisible gold, and may vary from mildly to highly refractory. Pyrite-telluride ores contain gold-bearing tellurides, and are refractory to varying degrees. Antimonial ores usually contain aurostibite, and may be very difficult to process. A classification scheme for metallurgical processing, based on mineralogy, is proposed for the ores, and implications for processing are discussed.

Jan 1, 1995

By Ken-ichi Machida

"Surface modification of R-Fe-N intermetallic compounds was made to improve their magnetic property and nitrogenabsorbing ability, arid high-performance resin-bonded magnets and nitrogen storage materials were developed: Surface coating for Sm2Fe11Nx by the zinc metal produced via photodecomposition of Zn(C2Hs)2 was effective to avoid the further oxidation in the molding process of the fine powders for bonded magnets and the resulting (BH)max values were improved to -186 kJm-3. Meanwhile, R2Fe17 as the mother compounds for RzFe11Nx was highly active for decomposition of NH3 molecule and subsequent nitrogen absorption as metal nitrides. Furthermore, even inert Nz molecule was dissociated on them by impregnating Ru metal and the resulting nitrogen atoms were absorbed in the crystal lattice of R2Fe17. These results demonstrated that the nitrogen storage system was established by cycling the nitrogenation and hydrogenation of RzFe11/R2Fe11Nx materials.IntroductionProcessing for rare earth metals and intermetallic compounds requires well-controlled conditions in order to avoid the oxygen contamination involved in it due to their high reactivity, as causes the serious damage for materials such as magnets, metal hydride for hydrogen storage, and so on. Rare earth-iron intermetallic compounds, R2Fe17, provide the corresponding metal nitrides (R2Fe11Nx) by heating in N2 or a mixed gas stream ofNH3-H2 [l] and, among them, Sm2Fe11N3 has been particularly noted as one of the promising materials for high-performance permanent magnets such as bonded ones [2- 6]. Usually, the nitrogenation for Sm2Fe17 is made in Nz, but it needs the much more hard conditions of reaction pressure (-10 MPa), temperature (-550°C) and time (-72 h) than the nitrogenation in the NH3-H2 mixture [l]. In the latter case, a significant amount of nitrogen can be interstitial introduced in· the R2Fe17 crystal lattice (x=-7) under the more moderate conditions than in N2 (at 0.1 MPa and -450°C for -3 h) [3-6] and then, in a similar manner as metal hydride systems [7], the excess nitrogen in RzFe1 7Nx (x>3) is reversibly desorbed by heating at a temperature around 500°C in Ar to form the RzFe11N3 compounds. This behavior of nitrogen absorption and desorption has a close relation to the sites for nitrogen in the crystal lattices."

Jan 1, 2000

By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000

By D. M. Hausen

Applications of process mineralogy to the exploitation of molybdenum ores begins with early exploration and continues through the evaluation of mineralized prospects, to amenability testwork and pilot plant studies, to the development of a mineable orebody and to the development of a viable process for recovery. After plant construction, a broad range of products from a wide selection of sampling locations, i.e. grinding circuit, flotation cells, smelters and roasting kilns. etc., are evaluated analytically and microscopically, followed by periodic troubleshooting of problem points. The various crystalline phases of molybdenum that occur naturally and throughout various hydrometallurgical and pyrometal1urgica1 processes are identified and characterized by a variety of instrumental methods, including XRD-XRF, optical and electron microscopy, infrared spectrographic and differential thermal analysis.

Jan 1, 1989

By Sheng-li Wu, Guo-liang Zhang, Bo Su

One of the major challenges for the Canadian Gen IV Super-Critical Water-cooled Reactor (SCWR) concept is the selection of fuel cladding materials. The Canadian SCWR concept will operate at a core outlet temperature of 625 oC and 25 MPa of pressure with peak cladding temperature reaching as high as 800 oC. Corrosion resistance is an important factor for material selection. Austenitic stainless steels that contain Cr contents greater than 18 wt.% are generally considered to provide adequate corrosion resistance. In this work, the pressure dependence of the corrosion of austenitic stainless steel 310 containing 24 wt% Cr is assessed at 625 C for exposures of 1000 hours to evaluate the suitability of superheated steam as a surrogate for supercritical water at 25 MPa. Transmission Electron Microscopy (TEM) revealed that 310 exposed to different pressure conditions at 625 oC. (i.e., 0.1, 8 and 29 MPa) had generally the same type of the oxide structure, i.e., a Cr-rich oxide with the spinel structure on outer surface adjacent to the water phase. The material exposed at 8 and 29 MPa had a double layer oxide structure, with the outer oxide layer having a much larger grain size, while the samples exposed at 0.1 MPa showed only a single spinel-phase oxide layer. Cr-depleted recrystallized austenite grains were found underneath the spinel phase oxide. The adjacent large-grained austenite substrate had M23C6 carbides in the grain interior. The implications of these results are discussed.

Jan 1, 2015

By C. A. Nogueira, F. Margarido

"A research work has being carried out annmg at evaluating the possibility of treating simultaneously several electrochemical systems of spent batteries using the same process, in order to overcome the high costs and difficulties of selective collection and sorting. Zn-Mn02 systems, representing more than 75% of portable battery market, shall be treated in dedicated processes. The treatment assessment using a single hydrometallurgical process of the other major systems (NiCd, NiMH and Li-ion), having Ni and Co as main metals, was the aim of the research work here reported. Sulfuric acid leaching was demonstrated to be adequate for dissolving more than 90% of the metals of interest contained in batteries. The subsequent separation of metals by solvent extraction, using organophosphorous extractants like DEHPA and Cyanex 272, allowed the production of pure solutions of rare earths, cadmium/manganese, cobalt, nickel and lithium, enabling their further recovering.IntroductionRecycling is the best approach for end-of-life management of spent batteries mainly by environmental reasons but also motivated by resources conservation and, in some cases, by economic profits. Most relevant electrochemical systems of portable cells are Zn-Mn02 (ZMB, alkaline and saline), nickel-cadmium (NiCd), nickel-metal hydride (NiMH) and lithium-ion (LIB). These batteries are collected, sorted and usually treated separately, applying for pyrometallurgical or hydrometallurgical technologies, the former being the most common.Several processes have been developed and some of them industrially applied, as described in some available review papers [l, 2]. In Europe for ZMB systems the oldest processes are Batrec [3] and Citron [4]. Although having differences in details, both are based on pyrometallurgical recovery of zinc by distillation, in metallic or oxide forms, being manganese retained in the slag together with iron. Hydrometallurgical alternatives are also available, like Zincex [5] and Recupyl [ 6] processes, both using sulfuric acid solutions as leachant. The application of the existing technologies to battery recycling, instead of using dedicated processes, is other alternative already tested, being the Waeltz furnace or the Imperial Smelting some examples."

Jan 1, 2012

By Norihiro Murayama

Syntheses of zeolitic materials were carried out from coal fly ash by alkali hydrothermal treatment as part of the reuse and recycle technologies of coal ash, For the obtained zeolites, the cation exchange capacity and acid resistance, which are very important in the practical use of cation exchanger in aqueous solution, are investigated during this stufY, The cation exchange amounts of the NaP, CaP and K-CHA zeolites are measured for various cations such as K+, Na +, NH4+ Ca2+, Mg2+, Pb2+, Cd2+ and so on. The change in crystallization degree are researched as a function of pH. The simultaneous removal ability of NH4+ and PO43- in solution is examined for an example of the water purification with CaP zeolite. From these results, the characteristic and its mechanism of cation exchange are clarified for the various zeolitic materials obtained from coal fly ash.

Jan 1, 2003

By M. L. Cunha

The lack of control of As and Sb compounds from copper smelters and converters has rendered some chalcopyrite containing arsenopyrite, stibnite and tetrahedrite minerals unusable for metal extraction. In the present investigation, we have studied the carbothennic reduction of Portuguese chalcopyrite mineral concentrate in the presence of lime/CaS04 and CaS04/Si02. Thermodynamic equilibrium calculations were performed to study the distribution of As and Sb between metal and the CaO-Si02-FeO slag phase. The phase equilibrium calculations also show the effect of oxygen partial pressure on the increase in the volume of the slag phase, which helps in lowering the copper metal formation temperature and facilitates a better separation between metal, matte and slag. The reduction reaction kinetics was studied between 850°C and 1100 °C, and the phases formed were identified by X-ray powder diffraction and scanning electron microscopy techniques. The importance of this research for using recycled matte, lean and rich minerals with As and Sb is also explained.

Jan 1, 2001

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 D. M. Jones

Dust generation data have been obtained from 19 industrial Outokumpu flash furnaces. Statistical analyses of the data have been carried out and the most significant factors affecting dust generation evaluated. The results indicate that dust production may most effectively be minimized by: 1) Minimizing the distance between the molten slag and the furnace roof 2) Optimizing burner design and combustion parameters.

Jan 1, 1996

By Z. Yang, R. W. Smith, Jr. Wharton

"Microorganisms have the ability to remarkably adsorb and/or absorb heavy metal ions. Hence they are being studied widely as a means of removing metal ions from aqueous solutions both in order to clean up toxic streams and to recover valuable metals from these and other streams. It is often difficult to harvest organisms such as bacteria and unicellular algae since they are usually too small to be readily screened out. Froth flotation may prove to be a feasible method to harvest such organisms subsequent to the ad/absortion of the metal Ions. The present paper discusses the surface/electrokinetic properties of microorganisms and the modifier-collect conditions under which they should float. The zeta potential of the green alga Chlorella vulgaris was measured in the presence of AI(III) and Pb(II) ions and in the presence of dodecylammonium chloride and sodium dodecylsulfate. Present and past data suggest that the organisms should behave similarly to other finely divided, charged (polar) solids with their behavior sometimes modified by the non-polar surface regions present.IntroductionThe overall field of bioengineering is growing at a remarkably accelerating rate. Hydrometallurgy and mineral processing are included among those disciplines where there has been actual or proposed commercial use of bioorganisms. Further, the actual or proposed use includes bacterial enhancement of leaching of a number of different types of ores (1-5), modification of the flotation or oil agglomeration separation of minerals by bacteria (6,7) and microorganism (algae, bacteria or fungi) concentration of metal ions present in effluent or other mineral processing or hydrometallurgy aqueous streams (8-23)."

Jan 1, 1988

By Jason H. Nadler, Jason A. Kulpe, Stephanie J. Lin

"A numerical method has been developed to predict the microstructural characteristics of reticulated metal foam. The porosity of this foam is derived from sacrificial template particles of known particle size distribution, which are incorporated with other precursor components. In this approach, a porous structure is numerically generated starting with Powell's sphere packing algorithm. The resulting stochastic structure has characteristics similar to those of corresponding metal foam. Deterministic inter-sphere connections are calculated to more accurately model the pore morphology that evolves during thermochemical synthesis. Estimations of pore morphology and specific surface area of the simulated material are compared to lab-synthesized materials composed of equivalent constituent compositions. In addition, the effect of template particle size, inter-sphere connections, and the geometric constraints on pore morphology and permeability are investigated to refine microstructural evolution and design.IntroductionReticulated foams, characterized by their interconnected pore network, can be obtained by incorporating spherical sacrificial template particles into precursor materials followed by template removal processes. The resulting structure is composed of contiguous spherical pores whose morphologies reflect those of the original templates. Based on some of the unique features of this synthesis approach, a methodology is introduced in this work whereby these foams are digitally constructed using experimental data from the template particle sizes and precursor formulation. Digitally constructed porous structures can then be compared to their laboratory synthesized counterparts through the quantification of structural features such as porosity and surface area per unit volume, which in tum are used to inform the foam's fluid transport propertiesThe spherical template particle packing algorithm developed here is adopted from Powell's work [1], which also includes approaches to obtain percolation and density in random packings [2]. Gervois gives a mathematical development for the stereological sectioning of packed hard spheres [3]. Stereological sectioning facilitates determination of relevant three dimensional morphological properties from two-dimensional data [4]. Studies on the sphere distribution size and the related particle packing density and coordination number results are studied in [5, 6]. Lastly, Kato describes a sintered neck structure, which is used with these packings [7]. This neck structure, as a model of the particle shape following heat treatment, is implemented here in a similar manner. A strong difference between the available literature and the methodology here is that spheres are packed to ultimately represent porous space, not rigid solid space."

Jan 1, 2011

By Z. M. Zheng

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

Jan 1, 1995

By Kevin L. Gering

A detection method and apparatus have been developed to perform real-time measurement of aqueous free cyanide, C-. A laboratory prototype can measure cyanide ranging from 5 micrograms ,per liter to 100 milligrams per ?liter for analysis times as short as 2 minutes per measurement. Sample size per measurement is typically only a few mI, thus? minimizing the waste volume produced from spent samples. The basis for this detection device is a quantifiable, stable affinity between the electrode material and free cyanide in the sample; The electrode exhibits piezoelectric behavior, allowing it to be used as a microbalance. This technology 'has experienced two generations of laboratory prototypes, and has been thoroughly tested to determine the operational sensitivity toward process variables such as pH, competing reactions, etc. The speed and ,accuracy of this method make it superior to conventional wet chemistry methods used for quantifying cyanide levels in water. A device based on this technology could be useful in areas involving process monitoring and environmental compliance, .particularly in the cyanide-based leach mining industry. Interest for this detector has been shown by the gold mining industry and others. Patent application is in progress.

Jan 1, 1998

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

By J. T. I. Poijärvi

The smelter off-gas cleaning and the weak acid treatment at Outokumpu Harjavalta Metals Oy are presented and described in this paper. The smelter consists of the copper and nickel smelters and the acid plant of three separate acid plants two of which are double contact and one single plant and of one liquid sulphur dioxide plant. The preliminary cooling and flue dust separation of the smelter off....,gases from the copper ?and nickel flash smelting furnaces and converters? in the waste heat boilers and in the hot electrostatic precipitators are described. The final cooling and cleaning of the gases in the scrubbers at the sulphuric acid plant and the treatment of the weak acid in the vacuum and in the submerged combustion evaporators for the removal of impurities are presented as well as the treatment of the condensates from the evaporators. The attention is paid to the generation of sulphur trioxide in the smelter off-gas.and to the treatment of that in the weak acid bleed-off and to the utilization of the treated acid.

Jan 1, 1992

By J. T. I. Poijärvi

The smelter off-gas cleaning and the weak acid treatment at Outokumpu Harjavalta Metals Oy are presented and described in this paper. The smelter consists of the copper and nickel smelters and the acid plant of three separate acid plants two of which are double contact and one single plant and of one liquid sulphur dioxide plant. The preliminary cooling and flue dust separation of the smelter off-gases from the copper and nickel flash smelting furnaces and converters in the waste heat boilers and in the hot electrostatic precipitators are described. The final cooling and cleaning of the gases in the scrubbers at the sulphuric acid plant and the treatment of the weak acid in the vacuum and in the submerged combustion evaporators for the removal of impurities are pre¬sented as well as the treatment of the condensates from the evaporators. The attention is paid to the generation of sulphur trioxide in the smelter off-gas and to the treatment of that in the weak acid bleed-off and to the utilization of the treated acid.

Jan 1, 1992