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By Rajashekhar Marthi

Lithium is a key component for future electric vehicle batteries and energy storage. The future availability of lithium to meet the growing demands remains in question. Around 60% of lithium resources exist in the form of continental brines. Traditional methods to recover lithium from brines use solar concentration with precipitation and have found limitations in lithium extraction due to interference of Mg in high Mg/Li brines. Thus, there is a need for highly selective adsorbents. Recently, spinel structured delithiated lithium manganese oxides have demonstrated promising results. However, due to the small particle sizes, it is economically difficult to recover the adsorbents and thereby limits industrial applications. In our work, LiMn2O4 ion sieve was synthesized and immobilized on diatomaceous earth. Fundamental adsorption studies were carried out in lithium buffer solutions to understand the nature of adsorption and kinetics. The adsorbents were also tested for recycle stability, as well as recovery of lithium from Great Salt Lake water samples.

By Yiling Zhang, Paul A. Salvador, Gregory S. Rohrer

"Photocatalysis utilizes solar energy to produce hydrogen by splitting H2O. When a thin film of photocatalyst TiO2 is supported on a ferroelectric BiFeO3 substrate (band gap ~2.5 eV), the TiO2/BiFeO3 heterostructure is capable of photochemically reducing Ag+ to Ag0 in aqueous solutions under blue light with enhanced efficiency. The observation of spatially selective silver patterns on surface of the heterostructure after reaction suggests that photogenerated electrons and holes in ferroelectric BiFeO3 are driven in opposite directions to reduce their chance of recombination. Comparisons of the amounts of reduced silver on TiO2 film grains with distinct phases/orientations show that the reactivity is mildly preferential on anatase TiO2 phase and does not strongly depend on crystallographic orientation of BiFeO3.IntroductionTitania (TiO2) is capable of photocatalytically converting H2O to hydrogen and oxygen under the irradiation of ultraviolet light. [1, 2] One of the limiting factors for titania to be used as an effective photocatalyst is its band gap. Because the absorption edges of rutile and anatase titania are at 3.0 eV and 3.2 eV, respectively, they can only absorb light in the UV portion of the spectrum, which is about 3% of the available solar energy. [3-5] This limitation has motivated attempts to modify the absorption edge of titania so that it can absorb visible light.One strategy is to substitute a portion of the titanium and/or the oxygen with other atoms. There are numerous reports on visible light absorption of titania by doping and co-doping of Cr, V, Mo, Sb, Fe, N, S, C, and F. [6-34] Another strategy is to add an adsorbed molecular species that absorb visible light and donate an electron or hole to the titania, such as organic dyes [33, 35, 36] and Ce3+/Ce4+. [37, 38]The strategy in the present work takes the approach of depositing a pure titania thin film on a visible light absorbing substrate BiFeO3 to induce visible light activity of the heterostructure. BiFeO3 is a semiconductor with a band gap of about 2.5 eV [39-41] and is photocatalytically active in visible light. [42, 43] It is also ferroelectric with spontaneous polarization along pseudo-cubic <111> directions of 6.1 µC cm-2. [44] The spontaneous polarization gives rise to internal electric fields that drive photogenerated charge carriers, namely electrons and holes, in opposite directions to reduce their chance of recombination. [45-47] Additionally, the separation of electrons and holes leads to the spatial separation of reduction and oxidation half reactions so that the back reaction of intermediates is also suppressed. Such charge carrier separation has been reported in TiO2/BaTiO3 heterostructures with UV light illumination. [48-51] The TiO2/BiFeO3 heterostructures in this work combine both advantages of the relatively narrow band gap and the internal fields in BiFeO3 to enhance the overall photocatalytic activity."

Jan 1, 2014

A comprehensive numerical capability for the analysis of Thermal Spray (TS) systems consisting of a three-dimensional compressible, turbulent flow Navier-Stokes model and a multi-phase particle flow model in Lagrangian formulation, was developed. This capability is validated for a set of flow conditions typical for TS. The developed methodology is used for analysis of the JP-5000 TS gun gas and coating powder flow conditions. Modeling and analysis of particle/turbulent eddies interaction is performed. Details of gas flow field, particle temperature, and particle velocity histories, and particle temperature, velocity profiles in the system are presented. For the validation of numerical analysis, the computed results are compared with available experimental measurements. The flow phenomena for different flow parameters are analyzed and explained as the results of gas dynamics and heat and momentum transfer between the gas and particle phases. This methodology can be used for process control and reliability improvement, and has the potential to significantly improve TS gun performance through control of its parameters.

Jan 1, 1996

By Xiaobing Yang, Abhishek Lahiri, Animesh Jha

"In the FFC-Cambridge process, the cathodic dissociation of oxide and CO/CO2 production on carbon anode is the basis for metal production in a CaCl2 bath. By using an inert intermetallic anode, the CO2 evolution can be eliminated altogether with acceleration in the electro-reduction kinetics. At present the process suffers from slow reduction kinetics of TiO2 to Ti metal, which can be enhanced significantly by the incorporation of alkali species in the TiO2 pellet at the cathode and in the CaCl2 bath in the presence of an intermetallic inert anode. Nearly full metallization with greater than 99% of Ti metal containing 1500 ppm of oxygen is possible to achieve in less than 16 hours of electro-reduction. Analyses of phase composition and the microstructures morphology in fully metallized pellets revealed the presence of localized solidified Ti layer, indicating that fast reduction process also involved formation of liquid phase as middle stage reaction. In addition, in situ creation of porosity and maintain higher current level during electrolysis process were two key factors to fully reduction of TiO2.IntroductionDuring cathodic dissociation of TiO2 in a CaCl2 bath and anodic evolution of CO2 on a carbon anode, which is the basis for the FFC Cambridge process [1], the rate of metallization slows down due to the formation of CaTiO3 at the reaction interface. Calcium and alkaline earth perovskites are known for their poor electrical conductivity which adversely affects the overall electro-reduction. One of the ways to increase the porosity is via the addition of polyethylene precursors in the pellet or by directly starting from perovskite [2, 3]. The experimental evidences shown in the literature confirm although the speed of reaction increases, but a complete or near complete metallization is not possible by enhancing the in-situ porosity alone, as the insulating perovskite is very slow to decompose under the equilibrium that prevails in the cell. Plethoric evidences on carbon anode show with the current decrease gradually, and finally stabilize at a very low value between 0.2 and 0.4 A, which is a testimony of the presence of perovskite insulating barrier in the current path. Our aim in this paper is to demonstrate the mechanism of enhanced electro-reduction when alkali ions are present in the oxide pellet at cathode and in the bath. We also show for the first time the use of an intermetallic anode for Ti-metal production using the FFC Cambridge process."

Jan 1, 2009

By Manuel Pérez-Tello

An experimental study on the oxidation of chalcopyrite (CuFeS2), pyrite (FeS2), covellite (CuS) and chalcocite (Cu2S) particles was conducted by means of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. Oxygen concentration in the process gas was set to 40 and 70% by vol. and a heating rate of 40 °C/min was used. Response variables included: the temperature of incipient reaction, the total exothermic heat of reaction, particle mass, morphology, and mineralogy of the reacted particles. Based on the experimental data and phase stability calculations, reaction mechanisms were proposed to represent the behavior of the particles during oxidation. The reaction mechanisms were verified by X-ray diffraction (XRD) analyses of the oxidized particles, and by thermochemical and mass balance calculations to reproduce the DSC and TGA thermograms. Overall kinetic models were developed to represent the evolution of the exothermic heat of reaction for each mineral as a function of time. Experiments conducted with copper concentrate particles containing the minerals studied suggest that the reaction mechanisms for the individual minerals can be used to represent the oxidation behavior of the copper concentrate particles.

Jan 1, 2006

By Bart Blanpain, Muxing Guo, Zhuangzhuang Liu

In order to stabilize free lime in the basic oxygen furnace (BOF) slag to achieve high value products, quartz sand and other additives are injected into slag. However, the current hot stage slag stabilization does not work in case of slag (before treatment) with a liquid fraction lower than 90%, where the slag containing solid particles is too viscous. Therefore, it is essential to understand how solid phases affect the viscosity of the slag system. In this study, the industrial BOF slags were investigated with respect to the correlation between volume fraction of solid phases and its viscosity. Slag viscosity was measured with a rotating type viscometer at temperatures below the liquidus. The volume fraction of solid phases was quantitatively calculated with FactSage. The Einstein-Roscoe equation was employed to predict the viscosity of BOF slag.

Jan 1, 2016

By R. G. Reddy

Reduction of different chromite ores with carbon was studied as a function of C/FeO ratio and temperature in the range 700 °C to 1100 °C by thermogravimetry (TGA) analysis. Powders of chromite ore(-150 mesh) and carbon(-150 mesh) were thoroughly mixed in a desired proportions and were placed in the reaction crucible. The reduction rates of reactions were determined by continuously monitoring the weight loss as a function of time at constant temperature using TGA set up. The analysis of results suggest that FeO present in the chromite ores is reduced to Fe involving gaseous intermediates CO and CO2. The overall rate of FeO reduction is controlled by the oxidation of carbon. A kinetic equation, that of random nucleation, was proposed. The activation energies for the reduction of FeO, present in Roast Movat and Transvaal ores, with carbon were determined to be 55800 and 23000 J/mole, respectively. The results of the present study are compared with the data available in literature. The low activation energy values as determined in this study suggest that the carbon oxidation reaction is catalyzed. It is concluded from the present investigation that the low grade chromite ores can be significantly upgraded to higher value added chromite that can be used as a feed source for economical smelting.

Jan 1, 1998

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By Qiang Zhong, Bin Xu, Qian Li, Yongbin Yang, Tao Jiang

Viscosity of slag determines the production efficiency, energy consumption and distribution of elements between metal and slag, which is very important for pyrometallurgy. Slag of goldantimony ore blast furnace smelting has seldom been studied. In this paper, the viscosities of gold-antimony ore smelting slags of different composition have been studied by the rotating cylinder method. The results showed that, for a slag of 38.95% SiO2, 16.17% CaO, 25.97% FeO, 10.25% Al2O3, 5.17% MgO, the viscosity can be decreased by reducing 3.24%-8.5% SiO2 or increasing 3.31%-9.56% CaO content. Complex SixOy z- from SiO2 acts as the main cause for the high viscosity in a slag of high SiO2. The increasing of CaO causes the decreasing of the amount of SixOy z- and the O2- dissociated from CaO breaks the complex SixOy z-, which can decrease the viscosity. Viscosity of different composition slag in the appropriate range temperature can be calculated from the Arrhenius equation.

Jan 1, 2015

By Volker Uhlenwinkel

The design of a free fall atomizer as well as the process parameters affect the particle mass flux distribution in the spray cone. The mass flux distribution is important in spray forming because of its influence on the deposit shape and enthalpy input into the deposit. In this article the effect of different process parameters on the mass flux distribution is shown. Furthermore, different melts were atomized with the same atomizer. An empirical correlation will be introduced to predict the mass flux in the spray cone. This correlation will be compared with experimental results.

Jan 1, 1999

By B. Yawney

A copper-nickel sulfide concentrate was leached in water at about 2000C under oxygen pressures of about 0.35 MPa. Oxidation of sulfide to sulfate was virtually complete in about 30 minutes, resulting in greater than 95% copper and 98% nickel extractions. Leaching temperature was shown to be the most important factor affecting metal extractions. Measured rates of oxygen consumption were used to develop batch kinetic data. Mini-plant continuous pressure leaching tests agreed with batch leach results. A proposed overall flowsheet is briefly examined.

Jan 1, 1976

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FexAs2O2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS203 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Miaoyong Zhu, Sen Luo

"A two-dimensional CAFD model was developed for simulating the solute diffusion-controlled dentritic growth in the low Peclet number regime. Mass conservation and local equilibrium at the solid/liquid interface were solved to determine the growth velocity of interface with consideration of constitutional and curvature undercooling. The modified decentered square growth proposed by Wang et al was adopted to capture the first eight neighboring cells. The comparison between the classic Lipton-Glicksman-Kurz (LGK) analytical model for steady state tip variables and the simulated values showed that the present model was capable of quantitatively determining the dendritic growth, and the simulation tests demonstrated that the effects of the mesh anisotropy in growth kinetics and crystallographic orientation were eliminated. The numerical simulations were performed to the dendritic growth ofFe-0.6%C binary alloy in undercooled melt, and the results showed that the present model could predict the dendrite morphology with artificial growth orientation in acceptable level.IntroductionDuring the solidification of metals and alloys, the dendrite grows from the substance or the undercooling melt and solute redistributes between the dendrite and the interdendritic liquid. The solidification microstructure is close related to the phase and solute evenness and has a close linkage with the properties of final production.In the past few decades, various kinds of deterministic and stochastic models have been developed to predict the evolution of microstructures in solidification, with the fast development of computer power. Among these methods, Phase Field (PF) model [1, 2] has been known as one of the most adequate deterministic models for directly simulating the dendritic growth. However, there is a vital drawback that the PF method requires considerable computation time and is limited to simulate very small domains with a few dendrites [3]. On the other hand, stochastic models, such as Monte Carlo (MC) method [4, 5] and Cellular Automaton (CA) method [6-8], have been usually applied to predict the solidification microstructure evolution. Comparing with the MC method, the dendritic growth kinetics is explicitly integrated in the CA model, while the MC model doesn't. Therefore, the CA method is more reasonable to predict the dendritic growth during the solidification of melt."

Jan 1, 2013

By Hong Yong Sohn

A novel flash ironmaking technology is under development at the University of Utah under the support of U.S. Department of Energy (DOE) and American Iron and Steel Institute (AISI). The history of the development from the conception of the idea to the current status will be discussed. The flash ironmaking process produces iron directly from fine iron ore concentrates without requiring cokemaking and pelletization/sintering, which will enable the technology to significantly reduce energy consumption and carbon dioxide emissions compared with blast furnace ironmaking. Unlike other gas-based ironmaking processes, this technology will not suffer from the problems of solid sticking and fusion. Current work is focused on the method of supplying the energy required to maintain the necessary temperature, as an intermediate step to determine the scalability for larger, industrial-scale pilot trials.

Jan 1, 2014

By Takamitsu Nakasuga, Haiping Sun, Kyushu University, Katsumi Mori

"The kinetic behavior of reduction of chromite ore by liquid iron containing carbon and silicon has been investigated under various experimental conditions to clarify the reduction mechanism. It was found that the reduction rate of chromium ore by liquid Fe-C alloy was very slow. In addition, when carbon and silicon coexisted in the iron melt, silicon was found to preferentially oxidized to form silica, which favored for the fonnation of liquid slag and the rate of reduction was considerably accelerated. The similar effect was obtained by the addition of some fluxes, such as SiO2, Na2B407, CaO-SiO2, which also promoted the formation of a liquid slag and thus the reduction rate in the early stage also increased.IntroductionThe reduction of Cr2O3 is a basic reaction for production of ferro-chromium from chromite ore and for chromium recovery from the slag fonned during the decarburization period of a stainless steel-making process. The reduction of chromite ore consumes much energy and its reaction rate is not so high. Thus, in order to increase the reduction efficiency, it is strongly desired to clarify its reduction mechanism from the practical and the theoretical points of view."

Jan 1, 2000

By M. El Ganaoui, P. Bontoux

"A computational model to investigate solid/liquid phase change transitions for binary alloy under directional solidification is presented. Conservation equations are developed by using an homogeneous formulation. A second order accuracy method of time and space based on finite volume approximation has been evaluated by comparing results to spectral solution for time-dependent solutal convection developping in a melted alloy. For extended model to solid/liquid interface effects time amplification of solutal perturbation injected near the interface is described before considering solutal convection is melt.IntroductionThe enthalpy method gives a front fixing approach for energy equation without introducing coordinate transformation. The interfare position is recovered a posteriori [1]. A number of authors have extended this approach so as to include the convection phenomena within the two phase 'mushy region' [2, 3, 4, 5, 6].We have developed a time-dependent enthalpy-porosity formulation for directional solidification [4, 6, 8]. The interaction between solid and liquid phases is modelised by a Darcien type force in the phase change area. The behaviour of the melt is similar with the flow of an incompressible fluid in a porous medium. This force is proportional to the relative phase velocity. It corresponds to a damping force depending on the anisotropic permeability of the 'mushy zone'. The permeability depends on the liquid fraction and on the size of·solidification microstructures. An informative discussion of a new slant on the general approach of continuum mechanics needed to analyze the formation of mushy zone is given in [12]. The method is extended to the presence of species diffusion: the solutal Stefan condition which expresses the solute incorporation or rejection across the interface is accounted implicitly in a species equation valid in all the domain [14, 15]."

Jan 1, 2001

By W. Murray Small

Nickel plays an important role in determining the properties of many stainless steels and superalloys. Cobalt also contributes significantly to the performance of certain grades of superalloys. A major technical aspect, in which both of these metallic elements are involved, concerns the solubility of nitrogen in these classes of alloys. Beyond certain content limits, dissolved nitrogen may contribute to the deleterious mechanical behavior by these alloys. It is therefore essential to control the level of this element during alloy processing. In this paper, results from several experimental studies have been assembled and are analyzed to describe phenomena related to the individual effects of nickel and cobalt on the solution of nitrogen in several groups of alloys. Both solid and liquid alloy systems are considered. This information may be used as a guide to limit or control the presence of this interstitial element in alloys.

Jan 1, 1993

By Hiroyuki Sano, Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa, Shin-ya Iwahori

"Pyrometallurgical process using Cu2O-based slag was proposed as a recycling process for copper scrap. However, it is difficult to remove nickel from copper by oxidative refining. Therefore, it is necessary to reduce the concentration of nickel in copper before the oxidative refining. In the present work, the copper enrichment stage in this recycling process, where copper scrap melt is separated into the Fe-C-Cu melt and the molten copper, was taken up and the compositions of both melts were measured. Based on the above results, the distribution ratios of nickel between the Fe-C-Cu melt and the molten copper were calculated. Furthermore, the optimum condition of copper enrichment stage was discussed from the viewpoint of nickel removal and copper recovery. The possibility of recovering 4N-purity copper by using this recycling process was confirmed.IntroductionRecycling is well known as a method for saving resources and reducing environmental damage. More than 99% of copper is used in metallic form - as metal or copper alloys[l]. High-grade copper scrap is directly re-melted and reused, while low-grade copper scrap is transported to copper smelters to be pyrorefined and electrorefined. Nevertheless, a great amount of copper is being stockpiled in the cities and should be recycled in the near future. At that time, the current recycling process will face new problems due to the increases in the recycling rate to the smelters. This includes insufficient combustion heat to melt copper scrap and ·almost no benefit in electrorefining because the scrap does not contain gold and silver. Thus, an alternative pyrometallurgical method for copper scrap refining will be required."

Jan 1, 2000

By Sepp Härkki

The energy crisis in Finland after World War I1 together with a sharp rise in the price of energy caused Outokumpu Oy to consider replacing the electric furnace smelting of copper concentrates by some other method. The flash smelting method developed under these circumstances offered a considerable saving of fuel through the utilization of the reaction heat of sulphides and yielded a high recovery of sulphur in the form of acid. The pilot plant testing of the new process was carried out in the years 1947 - 1948. The process was adopted for the smelting of copper concentrates (1) (2) (3) on a commercial scale in 1949 and applied successfullv to the smelting of -nickel concentrates&apos; at the Harjavalta Works in 1959 (4) (5) (6). In 1962 Outokumpu adopted another type of flash smelting where elemental sulphur is recovered from the gases after the thermal decomposition of pyrite in the flash smelting furnace (7) (8): In recent years, the copper-nickel flash smelter and pyrite process have been combined to produce elemental sulphur instead of SO2 from the smelter gases (9) (10). The basic idea of the Outokumpu flash smelting process for sulphidic ores is that the conventional methods with separate roasting and smelting operations are replaced by a combined roasting, smelting and part-converting process carried out in one unit. The heat generated from the exothermic reactions can thus be used for smelting the ore so that only a small amount of additional fuel is needed. The characteristic of the method is also that the dried, fine-grained concentrate is smelted in suspension, which offers the best conditions for rapid reactions. The recovery of waste heat from the furnace off-gases had been considered already in the original flash smelting system. A

Jan 1, 1976

By A. Navarra

Peirce-Smith converting (PSC) is applied for roughly 50% of primary nickel and 70% of primary copper production. PSC cycles produce batches of ironfree sulfide matte (or blister copper, in the case of copper smelters), that are subject to further processing. However, the number of cycles that can be performed simultaneously is limited by the offgas handling system. Moreover, PSC suffers from variation in the yield and duration of the cycles. This variation is managed by conventional smelter designs, in which the upstream smelting capacity exceeds the nominal converting capacity; PSC is thus a major bottleneck in conventional nickel and copper smelters. Stabilization and standardization of PSC operations can therefore increase smelter throughput. The current paper presents a discrete event simulation (DES) framework to assist in smelter debottlenecking. It features random number generation to represent cycle variability, and time-adaptive finite differences to represent thermochemical complexity. Preliminary computations are presented.