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By A. A. Trickett

In the treatment of gases from pyrometallurgical processes prior to acid manufacture, volatile components, sulphur trioxide and particulates ,are removed in wet gas cleantng systems. In the process a weak acid stream is generated, typically less than 10% H2S04, contaminated with volatiles such as arsenic, fluoride and chloride', plus metallic particulates. This effluent stream has, in the past, been disposed of in a variety of different ways. As a result of changing environmental legislation, smelters are having to review alternative solutions for treating this effluent stream. This paper' will describe a process developed by Chemetics which treats this effluent stream, generating a small dry metal sulphate stream plus a clean acid stream which is suitable for recycling to the smelter acid plant.

Jan 1, 1992

By Ch. -A. Gandin, M. Rappaz

"The grain selection mechanism which occurs during the growth of columnar dendritic structures is routinely used in the investment casting industry to produce directionally solidified (DS) and single crystal turbine blades. However, the evolution of the grain density with increasing distance from the chill has rarely been correlated with the evolution of the grain texture. This contribution presents a three-dimensional (3-D) stochastic modeling approach which permits the computation of grain maps, pole figures and grain density evolutions in DS superalloys. These predictions are compared with measurements resulting from an automatic indexing technique of Electron Back-Scattered diffraction Patterns. This 3-D stochastic model, which applies to uniform temperature situations, has to be extended to the dendritic growth in a thermal gradient. As a preliminary step, a 2-D Cellular Automaton (CA) has been coupled recently to Finite Element (FE) heat flow computations in order to predict the grain structures in complex shape investment cast part. The application of this CAFE model to the investment casting of a turbine blade is presented. Considering these results, the extension of the CAFE algorithm to three dimensions is discussed.INTRODUCTIONThe selection of columnar grains during the directional solidification of alloys plays a key role during the investment casting of directionally solidified (DS) and single crystal (SC) components for aerospace applications [I]. This selection mechanism, leading to a competition of the dendritic network propagation at grain boundaries, has been the subject of many investigations. In particular, the study of Walton and Chalmers [2] is remarkable since it provides a link between the evolutions of the density and of the texture of columnar grains with increasing distance from the mold wall. Since this original work of Walton and Chalmers, two new tools have become available, which enable one to revisit the problem of grain selection in much greater depth. The first one is a fully automatic indexing technique of Electron Back-Scattered diffraction Patterns (EBSPs) [3-6] which directly gives the crystallographic orientation of the solid at any location of the specimen. Pole figures, orientation distributions, misorientations between grains can be visualized very easily with this technique. This information can be directly compared with the results of a second tool: a three-dimensional (3-D) stochastic model (SM) describing the nucleation and growth of grains in a uniform temperature field [6-9]. In order to extend this model to non-uniform temperature situations, a preliminary 2-D model has been developed [10]. It is based on a Cellular Automaton (CA) algorithm coupled with Finite Element (FE) heat flow computations. Since the details of both the automatic indexing technique of EBSPs and the simulation tools have already been published [3-10], only a brief summary is given here."

Jan 1, 1994

By Koji Matsubara, Yoshiaki Iguchi, Shoji Hayashi

Iron ore particles of a limonite iron ore were reduced completely with H2 at 1023K to 1273K in a fluidized bed. Then, at 973K, the formed iron was exposed to HrH2S mixtures (sulfur activity, as=0.5) for 3.6ks and carbidized with CO-H2-H2S· mixtures at 0.1 MPa. During the carbidization, the particles of about 150mg were sampled at every 600s interval. The sampled particles were analyzed by XRD and chemical analysis for C and S to evaluate the content of Fe3C, Fe5C2, Fe and free carbon. The reaction extent is defined as fo=Xfc3C +xFc5c2; x is the molar fraction of Fe in Fe3C. The carbidization curves can be fitted very well to -ln(l-f0)=g(pb T)t; g(p; T) is the carbidization rate, i.e. the carburization rate on the pore surface of reduced iron. The rate is found to be nearly proportional to the specific surface area of reduced iron, a P 0 , which decreases with increasing the reduction temperature. The value of a P 0 does not change by the carbidization and the stability of the iron carbide product in the atmosphere increases with the temperature.

Jan 1, 2000

By Kazuki Morita

A new route to produce solar grade silicon (SOG-Si 6N) from metallurgical grade (MG-Si 98%) has been developed in Japan, which may satisfy the increasing demand for solar cells in the near future. Since some elements such as P and B have very large segregation coefficients, solidification refining is not effective for their removal and costly processes, such as electron beam vacuum melting and oxidation plasma refining, are required. According to our previous results which showed the effectiveness of leaching procedure with Ca addition for Fe and Ti removal, possibility of P and B removal by acid leaching was focused expecting that their affinities for Ca in molten silicon might be considerable. Hence, the effects of Ca addition on the thennodynamic properties of P and B in molten silicon alloys have been investigated for overall control and optimization of the SOG-Si production process in the present study. The interaction parameters between Ca and P, and Ca and B were determined by chemical equilibration techniques at 1723 K. Although the interaction parameter between Ca and B was slightly negative, that between Ca and P showed a large negative value. Also, the results for the leaching test with various amount of Ca addition revealed that the removal fractions of both elements, especially P, drastically increased with increase in the Ca content, which showed very good agreement with the prediction from the interaction parameters derived in the present work. The present results suggest that the preliminary leaching procedure can reduce the processing time and energy for SOG-Si refining. Keywords: Silicon, Solar Cell, Refining, Acid Leaching, Thennodynamics. Interaction, Phosphorus, Boron, Calcium

Jan 1, 2003

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of ilie cell at temperatures between 800 and 1100 K was measured. Whilc the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03V were found. It was difficult to determine temperature dependence of ilie Emf. The Gibbs energy change for the reaction, 113 LbN (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be tJ.Gor (LiMgN) -13.2 (±2.9) kJ/mol. Using thermodynamic information on ilie binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be AGO f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of ilie stability region of the LiMgN phase. The diagram was found to be in good agreement with the isoiliermal phase diagram determined by ilie alloy equilibration meiliod. Although the obtained data includes large uncertainties, the results provide a better understanding of the iliermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By M. S. Moats

The treatment of oxidized residues of zinc with high iron content continues to present a technical challenge in both the steel and zinc industries. Two main problems are commonly identified and include high treatment costs and environmental concerns about contaminated, iron-bearing residuals. A new approach to this problem is described in which selective separation of the iron and zinc into salable products may be potentially feasible. The waste material is first leached to give a solution having an approximate concentration of 110 g/l Zn, 15 g/1 Fe and 40 g/1 H2SO4 and other impurities such as Pb, Cd, Cu and Sb. A suitable organic, such as D2EHPA, is used to load the majority of the iron. The aqueous phase is then acceptable for zinc electrowinning after standard solution purification. The novel step in the flow sheet is the efficient recovery of the ferric iron from the organic solvent using a solid metal to reduce the iron to the ferrous state. The Fe+2 is easily stripped into an aqueous phase in a relatively pure form, suitable for use in water treatment. Process parameters and possible flow sheet designs are described and discussed.

Jan 1, 1995

By T. E. Warner

In order to detect arsenic and antimony in zinc, various electrochemcial experiments were performed involving the electrochemical introduction of sodium atoms into molten zinc using a solid electrolyte. Under high rates, the formation of the intermetallic phase NaZn13 was assumed to form. Under more moderate injection rates of sodium, employing a symmetric "zinc/zinc cell", a qualitative relationship between the current generated during cyclic voltammeuy and the arsenic and antimony concentrations in molten zinc was observed.

Jan 1, 1999

By Jing Zhan, Gui Li, Wei-feng Li, Li-Hua Jiang, Chuan-fu Zhang, Jian-yang Hwang

Thermodynamics analysis for processing the charge with lead concentrate and lead sulfate-containing materials in bottom blowing smelting furnace was conducted. The results show that the technology of large-scale processing PbSO4- containing materials with PbS concentrate in bottom blowing furnace under the condition of using high-iron slag type, batch heat supplement, high temperature and rich oxygen is thermodynamically feasible. The exploration test and industrial experiment confirm the results. When S content in mixed ore is 16~17% with coke foam content of about 5%, the lead paste amount can be increased up to 40%.

Jan 1, 2015

By Sudhir C. Dhara

An attempt has been made on the concentration of Platinum Group Metals (PGM) from the converter matte material by microbial .leaching. Biological oxidation of base metal sulfides such as iron, copper, nickel and free sulfur present in the matte material using Thiobacillus ferrooxidans is an alternative method to concentrate the PGM-and gold. The method which produces a platinum group metals concentrate is comparable to chemical processes and electrochemical process.

Jan 1, 1995

By Kandipati Sreenivasarao

A promising method for removing heavy metal ions from dilute effluents is ion- or precipitate- flotation, in which a suitable collector is added to form hydrophobic metal-collector complexes or compounds that can be collected as foams. We have successfully removed Cu(II), Cd(II), and Pb(ll) from dilute solutions using sodium dodecylsulfate and ethanol as collector and frother respectively. However the process would not be economically viable unless the collector could be recycled, and the heavy metals recovered in a concentrated, preferably marketable, form from the foams. We investigated four different methods to decompose heavy metal-dodecylsulfate complexes, namely precipitation of hydroxides, precipitation of sulfides, chemical stripping, and electrolysis. We compare the performance of these methods. In each case the observed behavior is related to known thermodynamic data, and potential applications are discussed.

Jan 1, 1995

By Kazuteru Tozawa

Surface tension, density and viscosity coefficient of acidic copper sulfate solutions simulating electrolyte solution for electrolytic production of copper have been measured and are summarized as a function of the solution composition and temperature. Nickel sulfatc is taken to be a representative coexisting sulfate that affects the physical properties of the copper sulfate electrolyte solution. The sulfates in the solutions, including sulfuric acid, increase the physical properties under consideration. Gelatin, representing organic additives for electrolyte solution, was found to sensitively affect the surface tension of the solution at low concentration of up to 200mgIL. The surface tension was markedly lowered by the addition of gelatin and the increasing concentration of gelatin led to a more pronounced decrease in the observed values. The surface tension gradually increases with time after addition of gelatin and the increase is enhanced by higher acid concentration and higher temperature. The observed change in the surface tension is considered to reflect the preferential adsorption of gelatin to the bubble-solution interface and the decomposition of gelatin due to hydrolysis to form various molecules having smaller molecular weights.

Jan 1, 2003

By Laura Garcia H, Juan Carlos Gonzalez Islas, Luis Garcia Lechuga, Pedro Alberto Ramirez Ortega

"Electrochemical studies were performed to silver recovery from industrial wastes (radiographic films) on litanium flat electrode using a filter press-type electrochemical reactor with vertical orientation (known as REOV-01), as counter electrode was used a mesh-type DSA. Voltammetric studies were employed to fmd the current range under which silver reduction occurs. Using chronopotentiometric studies with controlled current, homogeneous deposits were obtained on the surface of the Ti electrode, to a current of -210 mA during 120 minutes to a constant linear flow velocity of 15 Lmin-1 was achieved 97% of silver recovery from industrial wastes. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy studies corroborated the presence of silver on Ti flat electrode. In addition, the silver concentration in the solution after the experiments was 1 ppm below environmental requirements. This indicates the viability of a filter press-type electrochemical reactor with vertical orientation (REOV-01) for silver recovery from radiographic filmsIntroductionIn recent years, the industrial sector has shown an increase in the use of silver due to new applications in different areas. In sectors such as photography, the consumption of silver has declined as a result of the boom in digital photography. However, the use of silver in radiographic applications has not shown greater variation (47.16 Moz), as the image quality is essential for diagnosis in various fields, such as medicine. All the silver used in photographic applications is discarded completely (solid or in effluent). At the present, several countries have been involved in silver recovering from industrial wastes due to the economic value and environmental impact they represent. The main source of silver recovery is the wastes generated by the photographic sector. Various technologies have attempted to recover silver contained in these wastes. However, they have not fully satisfied the requirements of maximum recovery, nor environmental level (less than 5 ppm) of silver in effluents [1,2]."

Jan 1, 2014

By Kazuhiro Asai

Hitachi Refinery of Nippon Mining & Metals Co., Ltd. installed a reverberatory type recycling fumace in 1978 in order to treat the industrial wastes which contain metal elements such as copper, gold and silver. Pyrite and industrial waste materials such as galvanizing sludge, hydroxide slime and dust are smelted. Sulfidized copper, iron and precious metals are transformed into matte and other metallic elements are oxidized into slag This copper matte is transported to Saganoseki smelter and copper and precious metals in the matte are recovered. Recently it is difficult to obtain pyrite economically because of the decrease of pyrite production. Therefore, a new treating process of the liquid waste has been investigated at Hitachi Refinery. In this process, the sulfide or sulfate from the liquid waste are smelted as a source of sulfur.

Jan 1, 1997

By Guangliang Wu, Dongchang Huang, Xinbin Liu

Oxidation Kinetics of SPHC was analyzed by TGA, and the curve of oxidation weight gain with different temperature was acquired. It is found that, when the oxidation temperature is between 500 and 600 , all the curves are linear; when the oxidation temperature is above 700 , the curves are close to parabolic. At the temperature of 900 , the oxidation weight gain increases dramatically. The TGA results indicate that the activation energy of SPHC steel is 146.19 kJ/mol at the temperature of 500 900 , and an oxidation kinetic model was set up for variable temperature. Based on the temperature change during rolling process, numerical simulation of oxide scales evolution was carried out for SPHC steel, and the simulation result agreed well with measured ones. It can provide a basis for estimating the scale growth and controlling the temperature on site.

Jan 1, 2016

By Levente Becze

The zinc bottom dross is obtained as a by-product from hot dip galvanizing operations and contains at least 92 % zinc, which is recycled mainly by pyrometallurgical processes. The overall costs of such a treatment, however, are often relatively high, and the very strict environmental protection regulations might also cause additional difficulties for the high temperature procedures in the future. Therefore, a novel hydro-electrometallurgical process has been developed in our laboratory, by which one can reclaim zinc of high purity, while attempting to achieve low energy consumption and making allowances for all the environmental restrictions. This aqueous processing technique, based on electrolytic refining in a cell equipped with anion-exchange membrane to separate the anode and cathode compartments, allows the indirect purification of the anolyte. Zinc is dissolved from the anode along with some of the impurity elements, while the intermetallic compounds (Fe-Zn, Fe-AI- Zn) are accumulated in the anode slime.

Jan 1, 2003

By Warren J. Bruckard, Mark I. Pownceby, Sazzad Ahmad, M. Akbar Rhamdhani

Rutile is the preferred feedstock for producing high-grade TiO2 pigment but due to decreasing resources, alternative materials such as ilmenite is now used to produce a synthetic rutile (SR) feedstock. This requires removal of impurities (e.g. Fe, Mg, Mn) which, for a primary ilmenite is straightforward process. Processing of weathered ilmenite however, is complex, especially when chrome-bearing impurities are present since minor chromium downgrades the SR market value as it imparts color to the final TiO2 pigment, Chrome-bearing spinels are a problem in weathered ilmenites from the Murray Basin, Australia as their physical and chemical properties overlap with ilmenite making separation difficult. In this paper, different sulfidation process routes for weathered ilmenites are analyzed for their applicability to Murray Basin deposits as a mean of remove chrome spinel impurities. Thermodynamic and experimental studies indicated that selective sulfidation of chrome-bearing spinel can be achieved under controlled pO2 and pS2 processing conditions thereby making them amenable to separation.

Jan 1, 2015

By Y. A. Chang, J. Woodford, C. R. Kao

Reactive diffusion studies between NbC and Si were carried out at 1300 °C under a vacuum of 10-5 torr and a uniaxial pressure of 1 MPa. The annealing time ranged from 8 to 100 hours. The Si used was single crystal silicon; the NbC was hot-pressed powder compact. A NbSi2+SiC two-phase reaction layer formed with NbSi2 as the matrix and SiC as discontinuous particles. The microstructure of the reaction product is homogeneous, dense, and fine. The NbSi2 grain size and SiC particle size are in the micron range. The growth of the reaction products follows parabolic kinetics. Extrapolation of the data to zero thickness suggests an apparent incubation time of 3.5 hours. However, for short annealing time «60 hours), the thickness data can be approximated by linear kinetics with an initial growth rate of about 2 11m/hr. Based on these experimental observations, a growth mechanism for the reactive diffusion between Si single crystal and NbC powder compact is proposed. We propose that the nucleation sites for the SiC particles are at the voids of the NbC powder compact. This proposed nucleation mechanism offers a potential way of controlling the SiC particle size by changing the void size and void density of the NbC powder compact. This hypothesis, if proven to be true, will allow us to control mechanical properties of the composites by tailoring the SiC particles formed. It is also pointed out that the microstructure requires Si to be the dominant diffusing species and to diffuse through the reaction layer, while Nb and Conly have to undergo local rearrangement.

Jan 1, 1996

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By Ademar B. Lugão, Sandra R. Scagliusi, Elizabeth C. L. Cardoso

When butyl rubbers are subjected to high energy radiation, they form easy free radicals that initiate various chemical reactions. These reactions alter the molecular distribution of irradiated rubbers by crosslinking or scission affect their physical and mechanical properties. This work aims to the analysis of effect induced by γ-exposure on the crosslinking density in butyl rubbers by swelling measurements accomplished before and after irradiation at 25, 50, 100 and 200 kGy, with further evaluation of crosslinking density accomplished by Flory-Rehner equation; this is a proper procedure for the qualification of radiation resistance. It can be noticed that changes in material structure was due to build-up of new three-dimensional network in studied rubbers. Changes in crosslinking density of butyl rubber compounds emphasize that degradation mechanism is strongly influenced by gamma-radiation doses higher than 50 kGy, since chain scission process predominates over crosslinking reaction.

Mar 1, 2017

By Ray Y. Lin

This study explores the formation of sodium pyrosulfate in molten sodium sulfate resulting from dissolution of SO3 at temperatures between 1160 and 1250 K. Solubility of SO3 in Na2SO4 melts at temperatures between 1160 and 1250 K under gas mixtures of SO2, O2 and argon was investigated applying a thermogravemetric analysis (TGA) technique. The activity of Na2O in the melt was determined with a high temperature electrochemical cell (ECC). Results showed that the SO3 solubility in molten Na2SO4 increases with decreasing temperatures and increasing SO3 partial pressures. Enthalpy of SO3 dissolution in molten Na2SO4 was calculated to be -119 kJ/mol for infinite dilute solutions. Thermochemistry of Na2SO4-Na2S2O7 melts was analyzed based on information obtained from both TGA and ECC techniques. Detailed examinations of the earlier low temperature measurements in the Na2SO4-Na2S2O7 system along with data from this study reveal that the solution behavior between Na2SO4 and Na2S2O7 can be satisfactorily treated as regular with the interaction parameter, , being 2.7 kJ/mol. The phase diagram and the field of SO3 partial pressure has been generated with the thermodynamic calculation using a regular solution approach.

Jan 1, 2006