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By Nobuaki Sato, Tetsuo Fukasawa, Akira Kirishima

To apply the fluoride volatility process for the treatment of fuel debris formed in the damaged nuclear reactors, study on the fluorination behavior of main constituents, such as fuel and cladding is essential. The mixture of uranium and zirconium oxides is formed under severe conditions such as high temperature and oxidizing atmospheres. In this paper, fluorination and volatilization behavior of uranium and zirconium oxides have been studied by TG-DTA method in the presence of fluorine. From the TG-DTA result of UO2 in F2 atmosphere, the weight gradually increased up to 7% at 350 oC followed by rapid weight decrease with exothermic peak showing the vaporization of uranium as UF6. ZrO2 showed similar fluorination behavior to that of UO2. However, fluorination of UO2-ZrO2 seemed to be suppressed with increasing ZrO2 amount. This may be caused by the formation of solid solution.

Jan 1, 2016

By N. Kanari

The kinetics of oxychlorination of MgO by C12+02 was studied in the temperature range of 850 °C - 1025 °C, using thermogravimetric analysis. The effects of C12/02 ratio, gas velocity, temperature and partial pressure of reactive gases on the reaction rate were investigated. The oxychlorination process was characterized by an apparent activation energy of about 214 kJ/mol. The reaction orders with respect to C12+02, C12 and 02 at 950 °C were about 0.65, 0.98, and -0.37, respectively. Some data about oxychlorination kinetics of MgO, Cr2O3, and MgCr2O4 contained in chromite were compared. Efficiency of using oxychlorination for the removal of iron oxides contained in magnesia was demonstrated.

Jan 1, 1999

By R. N. O'Brien, E. Peters

"It has been discovered that copper concentrates can be leached in strong (40-60%) sulfuric acid with nitric acid, or with oxygen if nitric acid is present as a catalyst. Chalcopyrite is rapidly decomposed at temperatures well below the boiling temperature of the lixiviant (-150 C.) and the resulting copper and ferric salts are precipitated as CuS04.H20 and FeH(S04)z.4H20. Other metal sulfides such as zinc, lead, nickel, etc. are also converted to sulfates that are nearly insoluble. Sulfur is partially converted to elemental and partially to sulfuric acid. Reduction products of nitric acid can be recovered from the distillate with good recovery. Conversion of as-received copper concentrates is largely complete in about 1 hour. Introduction9 molar sulfuric acid is an unusual hydrometallurgical lixiviant: it has a boiling point of about 150 C. and a low solubility for base metal sulfates. Below about 6 molar acid, the boiling point falls below 120 C. and yields much higher sulfate salt solubility, while above 12 or 13 molar acid and at higher temperature sulfuric acid becomes an oxidizing agent, yielding gaseous S02' Thus, sulfuric acid within this range of concentration is capable of acting well above the temperature of boiling water without requiring autoclave conditions, and if typical oxidative leaching conditions are applied to suspended mineral sulfide concentrates, it is possible to obtain a conversion of these sulfides into 'crystalline sulfates. Thereafter, the sulfates can be separated by filtration or by solid - bowl centrifuge and the solution can be recirculated to the reactor vessel. Meanwhile, the solid sulfates can be treated in a typical hydrometallurgical circuit, i.e., dissolved in a return stream that is essentially water, separated from each other by, for example, solvent extraction, and recovered as metals by electrowinning."

Jan 1, 1997

By Maria D. Salazar-Villalpando, Anthony Cugini, Bryan Reyes

"The electrochemical reduction of CO2 was performed in a laboratory-made, divided Htype cell. A copper electrode was used as the cathode. An Aldrich Nafion 117-type ion exchange membrane (0.18mm thickness) was used as the diaphragm. NaHCO3 and KHCO3 were studied as the catholytes. Hydrogen evolution from water reduction and products from CO2 electrochemical conversion were recorded. Higher CO2 reduction enhancement was observed by KHCO3 as compared to NaHCO3. The main conclusion of this work is that in fact CO2 can be electrochemically reduced with copper electrodes.1.-INTRODUCTIONThe direct electrochemical reduction of CO2 may allow for a simple process and, by avoiding high temperature reactors, would enable the process production rate to be quickly varied to follow the time of day availability of surplus electricity [1]. Temperature has a major effect on the electrochemical conversion of CO2 since its solubility increases when temperature decreases [2]. The electrical potential applied to the electrochemical reacting system will have an influence on the product distribution, as well. For example, a narrow potential range during cyclo-voltagraphic studies will determine the detection of a lower number of products. A recommended potential range to study the electrochemical reduction of CO2 is -2V to 2V. Moreover, the reaction rate on the electrode is governed by various processes, such as the kinetics of electron transfer, adsorption/desorption at the electrode surface, and diffusion of CO2 to the Cu electrode. The availability of active species, CO2 for electro-reduction, is extremely low at the vicinity of the electrode surface and it seriously interferes with the rate of mass transfer. In batch type electrolytic reactors, depletion of CO2 at the surface takes place first. CO2 from the bulk then has to diffuse to the electrode surface, resulting in mass transfer controlled kinetic phenomena. During the above process, several other competitive side reactions could suppress the primary reaction even though the cathode has good electro catalytic properties for reduction of carbon dioxide. When the dynamic supply of specific active species is ensured to electrode surface, the mass transfer effects are minimized to certain extent. Hence it is envisaged that a continuous flow reactor is more efficient for the electro-reduction of CO2 in CO2 saturated aqueous electrolytes. The primary reactions that occur at the copper electrode during the reduction of CO2 are listed below (with the standard potentials calculated using formation energies [1] :"

Jan 1, 2010

By Thomas M. Harris

Cation exchange is not sufficiently selective to be used for the removal of heavy metal ions from a general industrial wastewater. However, if the metals can be converted to polyvalent anions through complexation, they may be removed both selectively and efficiently by anion exchange. This approach, referred to as chelation-assisted anion exchange (CAAE), has been examined using industrial wastewater samples contaminated with Ni2+ and Cr3+. For this particular application, the Ni2+ is complexed with 8-hydroxyquinoline-5-sulfonic acid, and the Cr3+ with sulfosalicylic acid. Removal efficiencies and adsorption isotherms for both the complexants and the complexes were determined in batch-mode tests.

Jan 1, 1994

By W. K. Tolley

The Bureau of Mines is investigating hydrometallurgical processing techniques to recycle metals from semiconductors and other advanced materials. Cadmium and tellurium were recovered from CdTe scrap produced in the manufacture of infrared optic devices. Sulfation, ferric chloride leaching, and oxygen-pressure leaching have been tested. Cadmium dissolution was achieved using oxygen-pressure leaching in dilute sulfuric acid. However, no satisfactory scheme for dissolution of the higher valued tellurium has been devised. Leaching the ground CdTe for 75 min at 110°C in 1.1M H2S0, under 120 psig 0, yielded 99.5% Cd extraction. Tellurium remained in the leach residue as TeO, and elemental tellurium; residual cadmium was less than 0.5%. The cadmium in the leach liquor was purified of coextracted metals such as gallium and iron by adjusting the pH. The cadmium was recovered as cadmium sulfate crystals by evaporating the solution. Recovery of by product metals, notably gallium, is possible.

Jan 1, 1991

By D. R. Spink

A partial desulfurization roasting (PDR) technique has been developed for use on zinc concentrates whereby the sulfide sulfur associated with the iron content is selectively removed over a very short residence ?time in the roaster. The resulting PDR product is then leached for the selective removal of the iron. The resulting leach restdite is an upgraded zinc sulfide concentrate which has a very low iron content. The up-graded zinc concentrate can be subjected to a conventional dead roast without formation of deleterious zinc ferrite so that hot acid leaching and jarosite (or other) iron precipitation steps are obviated. Examples are presented for the treatment of three very different types of zinc concentrates.

Jan 1, 1990

By Xinghui Meng

The recovery of platinum and palladium from automotive catalysts has been investigated by leaching in iodide solutions with oxidants including oxygen and iodine in an autoclave. An ammonium salt was presented in a neutral leaching solution as a key leaching reagent to achieve high recoveries of the platinum group metals (PGM). The effect of temperature, and concentrations of oxidants and of ammonium salt on the recovery of PGM was examined. Under the experimental conditions studied, the recovery of platinum and palladium was found to be greater than 95%. An economical assessment of this process has also been examined and discussed.

Jan 1, 1995

By H. J. Thevik, A. K. Dahle

"A mathematical model that calculates the stress development in a coherent and stationary dendritic network due to interdendritic flow is proposed. The fluid flow is assumed to be related to the solidification shrinkage, and under the assumption of no porosity formation and unidirectional solidification, the shrinkage-induced flow within the mushy zone is calculated analytically. The interdendritic melt flow exerts a force on the solid network and an analytical expression for the stress build-up in the network is developed. Parameter studies illustrating the influence of cooling conditions, mushy zone length, dendrite coherency, fraction solid, volume fraction of eutectic, and solidification shrinkage upon the stress development within the solid network are presented. Comparing the magnitude of the calculated stresses to measurements of the strength in equiaxed mushy zones shows that it is possible for the stresses to exceed the strength, thereby resulting in reorientation or collapse of the dendritic network.IntroductionInterdendritic fluid flow is at present regarded as a very important mechanism for feeding of shrinkage during solidification of metal alloys. Solidification of many alloys is often characterised by heterogeneous nucleation of the primary phase on substrates in the melt with subsequent evolution of equiaxed dendrites. These equiaxed dendrites can initially grow freely, but impinge on each other and form a continuous dendritic network, ie. dendrite coherency, quite early in the solidification process. Measurements of the dendrite coherency point have shown that the dendritic network is established at solid fractions ranging between 0.1 and 0.5, and most often around about 0.2 [l]. Depending on the alloy composition this means that as much as 70 to 80% of the volumetric shrinkage has to be compensated by flow of liquid through the interdendritic network. Interdendritic flow occurs with a much larger resistance compared to free flow of the liquid and flow of a liquid with dispersed crystals. The pressure drop associated with the interdendritic flow increases rapidly with decreasing fraction ofliquid."

Jan 1, 1999

By Raj P. Singh

Lewatit TP207, a chelating resin with iminodiacetate functional group, is used for the purification of cobalt hexammine chloride solution for divalent cationic impurities (US Patent No. 5,154,757). The method is employed at commercial scale in OSRAM SYLVANIA Inc. cobalt chemical production since 1992. It is observed that after long use in the purification of cobalt hexammine chloride solution, a large number of resin beads tum black from their original beige color. The purpose of this paper was to characterize these black-colored resin beads for their ion exchange behavior. The resin sample used in this work was an exhausted production TP207 resin containing large number of black-colored beads. The results indicated that blackened resin beads can be regenerated to almost full capacity and' their ion exchange behavior for the purification of cobalt hexammine chloride solution was comparable to the new resin.

Jan 1, 2001

By Kazuteru Tozcwa

The oxidation of several sulfide minerals in aqueous ammoniacal solution is discussed thermodynamically. The region in which Cu(NH3)2 4+ is stable has been estimated as a function of pH and concentration of total ammonia, {[NH3) + [NH4)}. In ammonia leaching when copper in sulfides is assumed to be extracted in the form of Cu(NH3)2 which will be rapidly converted to cupric ammine, thermodynamic data predict that such minerals are oxidized readily in the following order, CuS, Cu2S, CuFeS2, ZnS, NiS, Ag2S. This agrees with investigations on ammonia leaching of sulfide minerals, reported previously. The leaching of copper sulfide concentrate has been examined experimentally. Copper in a copper sulfide concentrate, in which the main constituents were chalcopyrite and pyrite, was effective¬ly extracted. The copper extraction was affected by factors such as (1) agitation intensity, (2) oxygen partial pressure, (3) NH3/Cu molar ratio, (4) leaching temperature and (5) addition of ammonium sulfate. From the results obtained in this work, it is concluded that mass transfer of oxygen plays the most important role in ammonia leaching of copper sulfide minerals.

Jan 1, 1976

By Andrzej Warczok

Liquid slags produced in smelting of copper concentrates contain copper in a dissolved form as well as mechanically entrained inclusions of copper matte. Coalescence and sedimentation of inclusions during slag cleaning plays a key role in copper recovery. Liquid matte inclusion in a molten slag presents a system of metallic conductor in an ionic solution. Constant electric field induces migration of the matte droplet along the current lines. Additional phenomena occur in a system under crossed electric and magnetic fields. Electromagnetic buoyancy force acting on the inclusion affects its settling rate. Electromagnetic buoyancy force of insulating and metal spheres has been measured in a liquid synthetic slag. It was found that depolarisation of the metal sphere, related to the electrode reactions occurring in the surface, plays an important role in the determination of the direction and magnitude of the electromagnetic force. On the basis of the existing theories and results of measurements a mathematical model describing the behaviour of metallic inclusions in the liquid slag under the influence of crossed electric and magnetic fields was developed. Simulation of behaviour of copper matte inclusions under crossed fields showed trajectory of motion in a liquid slag as a function of the slag properties and the inclusion size.

Jan 1, 2003

By T. Tamagawa

Vaporization of zinc and mixing of zinc vapor with CO-CO2 mixtures were studied experimentally to prepare Zn(g)-CO-CO2-Ar mixtures with desired composition for investigating the condensation behavior and efficiency of zinc vapor. The vaporization rate of zinc was generally constant under given conditions, and could be increased by raising the flow rate of the carrier gas, temperature and vaporization area. The Zn(g)-CO-CO,,-Ar mixtures were quenched by a water-cooling sampling tube for measuring the actual composition of the mixtures in the reactor. The oxidation extent of the zinc vapor in the CO-CO2 mixtures had relation to the CO2/CO ratios and the temperatures. Under current conditions, it was necessary to employ the CO2/CO ratio below 0.125 for mixing the zinc vapor with CO-CO2 mixtures without oxidation. In addition, the appearances and zinc contents of the condensed zinc on the sampling tube were also examined.

Jan 1, 2001

By R. F. Hammen

Copper is one of the most widely used metals in industrial processes and is also present in most mining operations. Extraction of copper from solutions often proves difficult due to the presence of complexing agents. ChromatoChem, Inc. has developed a Solid Phase Extraction (SPE) support (HiPAC) for removal and recovery of metals from wastewater. The HiPAC SPE support employs chelating agents covalently coupled to a long linker molecule. Several solutions containing copper and complexing agents were tested including 1) copper and carbonate, pH 9.8, 2) mixed metals and anions with copper and cyanide, pH 11, and 3) copper and the chelating agent EDTA, pH 11. The copper was extracted from solutions one and two at high pH, but the EDTA containing solution needed the pH lowered to make the copper available for capture. In each example, the copper concentration was significantly reduced by HiPAC SPE treatment.

Jan 1, 1994

By Takamasa Ishigaki, Gervais Soucy, Mohamed Rahmane

"The induction plasma jets employed for the in-flight nitridation of molybdenum disilicide (MoSi2) powders were investigated in terms of their flow characteristics. The present study shows the effect of the operating parameters of the plasma torch, as used for this process, on the plasma jet properties. The enthalpy probe techniques, along with mass spectrometry, were employed for the measurement of the jet temperature, velocity and concentration fields. The measured values were compared to the results of a numerical simulation performed on the plasma flowing inside the torch-reactor system. The process operating conditions studied were the plasma plate power, chamber pressure and sheath gas composition. The optimal conditions for effecting the nitridation process using thermal plasma are obtained at moderate plasma plate power, at around atmospheric pressure and by using a mixture of argon and nitrogen as the plasma torch sheath gas.IntroductionMolybdenum disilicide (MoSi2) based composites are considered to be one of the most promising candidates for high temperature structural material applications [!], especially because of their high melting points, good oxidation resistance and relatively low cost. However, the wide application of these composite materials is still limited by some factors such as their brittleness at room temperature and lower strength at high temperature (> 1500 K). To overcome such limitations, a number of researchers [2-4] have earlier studied various kinds of reinforcements for MoSi2, e.g. oxides, silicides and nitrides. More recently, Fan and coworkers [5-9] have demonstrated the possibility of in-flight nitridation and carburization of MoSi2, using a thermal plasma process. This work has confirmed the plasma synthesis route as one of the most promising methods for creating an in-situ second phase structure. Properties of the plasma flow, such as its temperature, flow velocity and composition, are of crucial importance for the nitridation of MoSi2 powders during their flight in the plasma. Therefore, the optimization of such a process involving plasma· generated reactive species necessitates a thorough understanding of the plasma flow characteristics."

Jan 1, 2000

By Klaus-Markus Peters, James G. Hemrick, John Damiano

"Work was performed by Oak Ridge National Laboratory (ORNL), in collaboration with industrial refractory manufacturers, refractory users, and academic institutions, to employ novel refractory systems and techniques to reduce energy consumption of molten material processing vessels found in industries such as aluminum, glass and pulp and paper. The energy savings strategies discussed are achieved through reduction of chemical reactions, elimination of mechanical degradation caused by the service environment, reduction of temperature limitations of materials, and elimination of costly installation and repair needs. Key results of several case studies resulting from US Department of Energy (DOE) funded research programs are discussed with emphasis on applicability of these results to high temperature processing industries.IntroductionRefractory materials are limited in their application by many factors including chemical reactions between the service environment and the refractory material, mechanical degradation of the refractory material by the service environment, temperature limitations on the use of a particular refractory material, and the inability to install or repair the refractory material in a cost effective manner or while the vessel is in service. All of these limitations reduce the energy efficiency of the process as degraded refractory materials lead to loss of process heat (reduced insulation by refractories) and the need for maintenance through repair or replacement of refractory linings.This situation is conceptualized in Figure 1 which shows that when the thickness of the refractory wall is reduced by chemical or mechanical degradation, the heat losses through the wall increase exponentially. The subsequent maintenance to repair such conditions often requires cooling of the furnace or refractory lined vessel which entails loss of energy due to cooling and consumption of energy due to reheating. Additionally, production time and capability are sacrificed.Additionally, in most applications where refractories are used (metal melting furnaces, glass furnaces, steel making furnaces, gasifiers, etc.) wear of the refractory lining is not uniform. Very often, specific areas will wear (become thinner) more rapidly due to exposure to more corrosive or erosive conditions. This concept is illustrated in Figure 2, through the example of excessive metal line corrosion."

Jan 1, 2009

By G. Scavino

A 0.5 wt.% C, 22 wt.% Mn austenitic steel, recently proposed for fabricating automotive body structures by cold sheet forming, due to favorable overall strength and ductility, exhibits plastic localizations during uniaxial tensile tests, whereas no localization happens during biaxial Erichsen cupping tests. Full-thickness tensile and Erichsen specimens, cut from as-produced sheets, were polished and tested at different strain rates. During the tensile tests, the plastic localization phenomena consist first of macroscopic deformation bands traveling along the tensile axis, and then of series of stationary deformation bands, each adjacent to the preceding ones; both types of bands involve the full specimen width and yield macroscopically observable surface relief. No comparable surface relief was observed during the standard Erichsen tests. The stress state being known to influence plastic localization phenomena, reduced-width Erichsen tests were performed with 10 to 30 mm width polished specimens, in order to explore the transition from biaxial to uniaxial loading.

Jan 1, 2009

By Daoxin Wu

In this paper, the rutile TiO2 were prepared under air, Ar and H2 calcination atmosphere by low temperature hydrolysis using Tetrabutyl titanate (C16H36O4Ti) as raw material. Powers were characterized by X-ray diffraction, UV-vis diffuse reflectance and X-ray photoelectron spectroscopy. The influence of the calcination atmosphere on the photocatalytic reactivity of rutile TiO2 for oxygen production was investigated. The photocatalytic reactivity of rutile TiO2 prepared under air, Ar and H2 atmosphere was compared under ultraviolet and visible light radiation with Fe3+ (c=8.0mmol.L-1) as electron acceptor. The results showed that rutile TiO2 prepared under Ar and H2 atmosphere had higher photocatalytic activity for oxygen production than that prepared under air atmosphere. The oxygen production rates under ultraviolet irradiation were 427.5, 378.2 and 357.0µmol.l-1h-1 respectively when rutile TiO2 was prepared under Ar, H2 and air atmosphere. The oxygen production rates under visible light irradiation were 78.2, 52.2 and 13.5µmol.l-1h-1 respectively when rutile TiO2 was prepared under Ar, H2 and air atmosphere.

Jan 1, 2008

By J. N. Kondo, M. Hara, T. Smida, N. Ooto, K. Domen

"A porous material composed of two-dimensional anionic sheets of a layered perovskite, KSrNb30 10, was studied as photocatalyst for the production of Hz in the presence of alcohol sacrificial donors. Colloidal single and multi-layered HSr2Nb30 10 sheets were formed by intercalating ietra(n-buthylammonium) cations into the interlayeres of H+-exchanged KSr2Nb30 10 (HSr2Nb30 10), and addition of HN03 solution to the colloidal suspension precipitated the porous materials in which HSrNb30 10 sh~ets rand~mly stuck together. Original HSr2Nb30 10 before exfoliation had a BET surface area of 1 m2 g-1, whereas the surface area of a porous material prepared under optimal conditions exceeded 100 m2 g-1. The porous HSr2Nb30 10 had considerably higher photocatalytic'activitie8 for oxidation of 1-propanol and 1-buthanol than HSr2Nb39io, indicating that in the porous materials many niobate sheets are available for decomposition of these large alcohols.IntroductionQuite a research effort has gone into the design and study of porous materials. Such materials with large surface areas would have applications in highly efficient adsorbents or catalytic reactions.We have been studying photocatalytic reaction by cation-exchangeable layered metal oxides, where alkali metal cations are intercalated into the interlayers of inorganic sheets.[1,2] There are several advantages to using layered compounds rather than bulk powders for photocatalysis. Layered compound is rich in variety, in addition, modifications of them are easily performed by exchanging alkali metal cations in the inter layers for H + or other metal cations. The most important advantage is that some layered compounds have considerably high photocatalytic activities than bulk catalysts because the electrons and holes generated in each thin inorganic sheet readily reach interlayer spaces as reaction sites at the illterlayer spaces. It should be very important for further improvements· of layered photocatalysts to utilize two-dimensional inorganic sheets effectively."

Jan 1, 2000

By Huanmei Yuan, Yuanyuan Wang, Hao Bai

Composite phase change materials are widely used in energy-saving and energy efficient process. Nano-encapsulated phase change materials are especially significant for making advanced working fluid applicable to waste heat recovery or storage. In this study, silica-coated stearic acid (SA) Nano composite phase change materials were prepared from tetraethyl orthosilicate (TEOS) and stearic acid (SA) via sol-gel process. The materials were investigated by Field emission scanning electron microscopy (FE-SEM), Transmission electron microscope (TEM), Fourier transform infrared spectroscopy(FT-IR) and Differential scanning calorimeter (DSC).The FE-SEM and TEM results show that monodisperse microspheres with stable core– shell structure were formed and SA was encapsulated in the silicon dioxide shell. The FT-IR results show that there were no chemical reaction between silicon dioxide and SA, which is the chemical property of the composite material, is stable. The DSC results show that the composite phase change material has favorable heat capacity.

Jan 1, 2016