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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 Qingchun Yu, Baoqiang Xu, Yongnian Dai, Bin Yang, Fulong Zhu

"In this paper, the mechanism of the carbothermic reduction-chlorination process to extract aluminum from alumina in vacuum was investigated. The carbon monoxide (CO) content of the gas, phases of the reduction slag, surface morphology of the reduction slag and the product aluminum were measured by means of gas chromatography (GC), XRD, and SEM. The experimental results indicated that the content of CO in the gas decreased, but Al4C3 increased with time at 1773K during the carbothermic reduction process of alumina. AlCl(g) and graphite (C) were produced by the reaction between Al4C3 and AlCh(g) at 1773K, and then aluminum beads generated after the decomposition of AlCl(g). It implied the mechanism of alumina carbothermic reduction-chlorination process in vacuum involves three steps as follows: the carbothermic reduction of A}z03 to produce Al4C3, the chlorination of Al4C3 by AlCh(g) to produce AlCl(g), and the decomposition of AlCl(g) to produce Al(l).IntroductionAluminum is the basic raw material for many industries [1], and it is used extensively because of various excellent properties such as light weight, good malleability, high strength, excellent thermal conduction, high corrosion resistance and so on [2]. Industrial production of aluminum currently includes refining alumina and electrolytic aluminum processes. However, its development has been effected by some factors such as high energy consumption and heavy environmental burdens [3]. In the past several decades, there had been numerous attempts to produce aluminum by new methods. Extracting aluminum from alumina or bauxite directly by carbothermic reduction-chlorination process had been studied [ 4-6]. Although the alumina carbothermic reduction process [7~9] had been studied, the mechanism of the carbothermic reduction-chlorination process had not been systematically elucidated.In order to investigate the mechanism of the carbothermic reduction-chlorination process in vacuum, GC, XRD and SEM techniques will be used to determine the CO content and to characterize the surface morphology and composition of the slags at various temperatures."

Jan 1, 2011

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 Bhagyadhar Bhoi, Chitta Ranjan Mishra, Hara Prasanna Mishra

"In the Sukinda Valley of Orissa, India, the total quantity of nickel ore reserves comprising of both lateritic and chromite over burden(COB) have been estimated at around 231 million tonnes containing 0.3 to 0.9% Ni. While mining of one tonne of Chromite ore, around 6-7 tonnes of chromite over burden are removed. These overburden materials are disposed as waste materials, which causes lot of environmental hazards and ecological imbalance. India imports a large amount of nickel and ferro-nickel to meet its growing demands in various sectors. For import substitutions, efforts have been made to produced ferro-nickel from the lean deposits of nickel bearing lateritic ores/ chromite over burden materials by reduction roasting followed by magnetic separation and then the nickel rich magnetic fraction is smelted to produce ferro-nickel. It has been possible to produce ferro-nickel of grade varying from 4-25% nickel.IntroductionDuring mining of chromite ore, large quantities of overburden materials are being generated. The materials amount to approximately 10 million tones per year contain around 0.3-0.9% Ni, 0.02-0.06% Co, 20-50% Fe and 4-9% Cr2O3 depending upon the location and the depth of the mine. These materials presently do not find any application for the extraction of nickel due to lack of a suitable technology. The materials are also unsuitable for ferro-nickel making because of their very high iron to nickel ratio. The country is seriously looking for a suitable technology to utilize these resources as its entire domestic requirements of nickel is met though imports. In this connection, a systematic approach has been made at the Institute of Minerals and Materials Technology, Bhubaneswar to develop a process for ferro-nickel making from this indigenous resource."

Jan 1, 2011

By Naixiang Feng, Shaohu Tao, Zhihui Wang, Yuezhong Di

"A novel vacuum aluminothermic reduction lithium process was developed in present work which used lithium carbonate, alumina and calcium oxide as raw material. The process mainly contained three steps. The first step is that LiA102 clinker is prepared in ambient environment, then metal lithium is vacuum extracted from LiAl02 clinker with aluminum power as reducing agent, and the last step is that alumina is leached from the reduction residue with a mixture of sodium hydroxide and sodium carbonate. The results show that the lithium reduction ratio can be over 95% under the conditions of reduction temperature 1423K, reduction time 3h, and aluminum excess 20%. The main components of reduction residue are CaO· Al203 and 12Ca0·7Alz03. The alumina leaching rate of calcium aluminate in residue is over 80%. High-whiteness aluminum hydroxide can be obtained by carbonation precipitation of the reduction slag leaching solution.IntroductionWith a density about half of water, lithium is with the lowest density of all solids, mere 0.5 g/cm3 at 20 °C [l]. Lithium is widely used in aerospace, aviation, nuclear-generated power and electric battery industry. Nowadays, over 90 % of the world's primary lithium is produced by molten salt electrolysis [2-4]. But the development of molten salt electrolysis will be effected by some factors: cost, environment, and so on. Vacuum thermal reduction may be used extensively in future because of its low-energy consumption, high-purity and short-cycle."

Jan 1, 2013

By Jewel Gomes

Produced water (PW) is salty water trapped in the reservoir rock and brought up along with oil or gas during production. It subsists under high pressures and temperatures, and usually contains hydrocarbons and metals. Therefore, it must be treated before being discharged to surface water. Different techniques are being used to treat PW through phase separations, system control and design, and chemical treatments. In this paper, we discuss our experimental results on treating PW through electrocoagulation (EC). The performance of EC was investigated for the reduction of chemical oxygen demand (COD) and metal ions. Effects of different electrodes, residence time, current density, and pH were also studied to optimize the treatment conditions. Different kinds of cleansing agents, such as lime and borax were used to break the buffering effect encountered during treatment. FTIR, SEM/EDS, and XRD were used to characterize the EC-floc and thus to elucidate removal mechanisms.

Jan 1, 2009

By P. R. Taylor

Laboratory experiments have been performed to evaluate the kinetics of roasting pyrite and arsenopyrite in air at elevated temperatures, in the presence of lime. The effects of temperature, time, air flow rate, particle size, lime type, and mineral/lime weight ratio on the rates of oxidation, lime sulfation, and lime arsenation were studied. The reaction products were identified using chemical analysis, x-ray diffraction, SEM analysis, and optical microscopy. The results are discussed in terms of the utilization of lime to capture sulfur and arsenic during the roasting of refractory precious metal concentrates. More than 99.9% of the arsenic and 98% of the sulfur are contained when roasting pyrite and arsenopyrite with hydrated lime under typical roasting conditions.

Jan 1, 1991

By Corby G. Anderson

In nature, mercury is quite commonly found in association with antimony ores. This can be as a separate mineral such as cinnabar or in direct association with the antimony ore. The most common antimony-mercury mineral is livingstonite that occurs in places such as Algeria, Mexico, USSR and China. In the Roznava deposit in eastern Slovakia, tetrahedrite ore containing mercury ore has historically been processed pyrometallurgically for its silver and copper values. As well, in Tajikistan, major antimony deposits there contain significant mercury ore concentrations within the stibnite ore body. The mercury contained in these materials poses both a processing and environmental challenge. This paper will outline the processing of these types materials by industrial alkaline sulfide hydrometallurgical methods. The economics relevant to this potential application at Roznava in Slovakia will be outlined.

Jan 1, 2003

By Richard D. Hangi

Process mineralogy techniques are uniquely applicable to industrial problems related to the extractive metallurgy of nickel, cobalt, and associated metals. Reflected 1ight microscopy, together with selected determinations by scanning electron microscopy-energy dispersive spectrographic analysis and electron probe microanalysis, provides the means to identify the ore minerals cobalt and nickel ores, determine the abundance of each ore mineral, assess the extent of intergrowth between the cobalt and nickel minerals and other ore and gangue minerals in the ores and concentrates, and predict the potential success of cobalt and nickel extraction by grinding, flotation, pyrometallurgical, and hydrometallurgical treatments. In addition, the extent of locking of the cobalt and nickel minerals with each other and with the gangue minerals can be directly observed by reflected light microscopy. Where ores have been treated by hydrometallurgical procedures, reflected light microscopy can serve to determine the causes of excessive leach consumption. Finally, the partitioning of cobalt and nickel between high-temperature synthetic phases produced by pyrometallurgical treatment can be precisely determined by process mineralogy techniques. Case histories from cobalt and nickel deposits illustrate the value of applied mineralogical techniques in the study of cobalt and nickel ores, beneficiation, hydrometallurgial, and pyrometallurgical products.

Jan 1, 1993

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 Junfu Chen, Jiann-Yang Hwang, Yong Zhou, Lijun Lu, Likun Lia, Jixiong Liu

The sheet-like NiS-ZnS heterostructured composites were prepared by the microwave hydrothermal. The fabrication of the heterojunctions broadened the range of light response of ZnS. The photoexcited electrons of ZnS migrated to the redox potential of NiS/Ni2S under visible light irradiation, which can facilitate the effective separation of photogenerated electrons and holes in space. The visible photocatalytic activity towards hydrogen production for NiS/ZnS nanosheet heterostructed composites without co-catalyst achieved 0.28 mmol h–1, and the quantum efficiency was up to 18.6% under the wavelength with 420 nm visible light irradiation.

Jan 1, 2015

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 James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades_ EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized_

Jan 1, 2003

By R. G. Reddy

Nickel solubilities in spent pickling solutions (i.e. HF-HNO3-H2O solutions ) were measured as a function of HF and HNO3 acid concentrations. The chemical analysis of the industrial pickling solutions and sludges were made. The stable phases observed in the sludges are FeF3?3H2O, and ( FeCr ) F3?3H2O. Pure Ni, and stainless steel type 316 were used in this study. The results showed that the solubility of Ni increased with increase in concentrations of HF in pickling solution at a fixed concentration of HNO3: An excellent agreement between the experimental solubility data and the theoretical data was obtained. X-ray diffraction analysis showed that the solid solubility product formed is mainly NiF2?4H2O compound.

Jan 1, 1992

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 Jack S. McPartland

The recent developments on the concentration and recovery of gold from leached gold thiosulfate solutions by solvent extraction, reduction-precipitation, and electrochemical deposition are reviewed in this paper. Alkyl phosphorus esters have been found to extract gold only in alkaline thiosulfate solutions, The recovery of gold increases with thiosulfate concentration in the aqueous phase and with alkyl phosphorus esters concentration in the organic phase with aliphatic hydrocarbon diluents. The addition of ammonia improves the extraction. The extraction of gold with amines in either aliphatic or aromatic diluent decreased in the following order: primary>secondary>tertiary amines. Increase in the extractant concentration at high pH increased the extraction of gold. At pH < 9, the primary amine, RR&apos;CHNH2 with 1&apos;9-23 carbon atoms is the main extractant with TBP as the synergistic reagent and at pH >9, the primary amine shows a synergistic effect on the extraction of gold&apos; with TBP. TheAu(I) ions in thiosulfate solution are reduced by sodium borohydride (SBH) to metallic gold, with particles in the sub micron range, At an SBH/ Au ratio of 6.25, pH = 6, and at room temperature, the I e ppm Au(I) in a solution of ] 0 gil thiosulfate was completely reduced to metallic gold in about 60 minutes.

Jan 1, 1999

By Hassan Saalman, Mahmoud Mahmoud, Omneya El Hussaini

The Ferruginous sandstone ore was obtained from Ramlet Hemeyir area, Southwestern Sinai, Egypt, was found to contain 10% rare earth elements (REE). A representative sample has been subjected to sulfuric acid agitation leaching. About 93% of the REE content was released by mixing the ground sample to -100 mesh with concentrated H2SO4 at solid/liquid (S/L) ratio of 1/2 for 5h at a temperature ranged from 250 to 300o C. The REE was precipitated from the prepared sulfate leach liquor of pH 1.0 by adding 35% oxalic acid at 25o C. The precipitation yielded 98% REE. For selective separation of yttrium, the rare earth cake was leached with 31.5% nitric acid. Next, the aqueous solution was contacted with di-(2-ethylhexyl) phosphoric acid (D2EHPA) where 98% yttrium extraction was achieved. Stripping was done with hot H2O (80o C). Finally, a precipitation with oxalic acid was done followed by ignition at 950o C. A yield of 95% yttrium oxide was produced.

Jan 1, 2014

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

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 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