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By Junji Shibata

The waste acid mixture whose main component is phosphoric acid, is discharged from the etching process in the liquid crystal production industry. In order to separate impurity acids from the phosphoric acid, trioctyl phosphate (TOP) is used as an extractant. TOP can extract acetic and nitric acids selectivity. The extraction and stripping operations are carried out for the acid mixture by beaker-scale experiments and countercurrent multistage operations with mixer-settler equipment. TOP selectively extracts the acetic and nitric acids in the acid mixture. From the results of the McCabe-Thiele analysis obtained by beaker-scale tests, the extraction for acetic and nitric acids are approximately 100%, respectively, by 6-stage extraction with a phase ratio (A/O) of 0.4. On the other hand, almost all of acetic and nitric acids are stripped with water from the organic phase by 4-stage stripping with a phase ratio (A/O) of 1.0. About 95% of acetic and 98% of nitric acids can be removed from the acid mixture without extracting phosphoric acid in case of the mixer-settler equipment operation. There are several steps such as slicing, lapping, chemical etching and mechanical polishing in the silicon wafer production process. The chemical etching step is necessary to remove any damaged layer caused in the slicing and lapping steps. The typical etching liquor is the acid mixture comprising nitric acid, acetic acid and hydrofluoric acid. The waste acid is treated by a neutralization method with a high alkali cost and balky solid residue. A solvent extraction method is applicable to separate and recover each acid. Acetic acid is first separated from the waste liquor using 2-ethlyhexyl alcohols as an extractant. Then, nitric acid is recovered using TBP (Tri-butyl phosphate). Finally hydrofluoric acid is separated with TBP solvent extraction. The expected recovered acids in this process are 2mol/L acetic acid, 6mol/L nitric acid and 6mol/L hydrofluoric acid. The yields of this process are almost 100% for acetic acid and nitric acid. On the other hand, it is important to recover and reuse the metal values contained in various industrial wastes from a viewpoint of environmental preservation. Most industrial products are made through processes to separate impurities in raw materials, solid and liquid wastes being necessarily discharged as industrial wastes. Chemical methods such as solvent extraction, ion exchange and membrane separation, and physical methods such as heavy media separation, magnetic separation and electrostatic separation are considered as the methods for separation and recovery of the metal values from the wastes. Some examples of the application of solvent extraction to the treatment of wastes such as Ni-Co alloy scrap, Sm-Co alloy scrap, fly ash and flue dust, and liquid wastes such as plating solution, the rinse solution, etching solution and pickling solution are introduced.

Jan 1, 2003

By U B. Pal

Downsizing and decommissioning of nuclear facility operations is increasing the stockpile of various different grades of Radioactive Scrap Iron (RSI). Disposal of this material not only represents significant resource and value lost, but also necessitates long term monitoring for environmental compliance. The latter results in additional recurring expense. It is desirable to be able to decontaminate the RSI to a very low level that can be recycled or used for fabrication of containers for RSI disposal instead of using virgin metal to fabricate the container. Electro-Slag Remelting and Refining (ESR) is often used for decontaminating radioactive contaminated sources of scrap iron such as stainless steel. Non-radioactive oxides of cerium are used to simulate the radioactive oxide contaminants of Uranium and Plutonium. The success of the ESR process is strongly dependent on the capacity of the slag to rapidly incorporate the radioactive contaminant (simulant). In this study we have measured the slag-metal partition coefficient for cerium and investigated the reaction mechanism for the dissolution CeO, in the slag.

Jan 1, 2002

By Wenliang Cao, Jidong Li, Mingjie Zhang, Yiyong Wang

In CaC12-CaF 2 System, we studied the electrode process and discharge mechanism of preparation of Al-Ca alloys by fused salt electrolysis with CaO as raw material. The change of back electromotive force after adding CaO was measured by continuous pulse oscillograph method and the discharge process mechanism was also investigated by cyclic voltammetry. The finial results indicate that back electromotive force decreases by 0.6V after CaO of 1 % is added and there was a peak of oxidation current ahead of the potential at which the negative chlorine ions precipitated. According to thermodynamic calculation, it was determined that current peak was caused by the CO2 produced by 0 2 - ionic discharge due to CaO addition.

Jan 1, 2014

By Masayasu Kawahara, Toshiyuki Kozuka

"Lorentz force, which has the functions of wave suppression and mixing control, is very useful for many metallurgical processes. In this paper, it is found that vertical Lorentz force which can change 'the gravitational force is able to modify the dispersion relation of the surface wave generated by gravity and also modify the instability phenomena on the interface so that the lower layer can be scattered into upper layers to realize the strongly mixed region.IntroductionIn metallurgical industries, recently, a new direction of process developments is required backed not only by severer operating conditions, e.g. small amount production, rapid refining, etc. but also by environment and energy problem. Because almost technologies in conventional processes have saturated, an innovative process, which can break the limits in the conventional processes, is now strongly required. Especially, controlling of mixing phenomena between two liquid phases is considered to be one of the most important technologies for the promotion of slagrnetal reaction, wave suppression, etc. On the other hand, electromagnetic forces which have various functions have been applied to many processes. And Lorentz force is able not only to suppress the wave motion of molten _metal surface but also to promote the mixing or separation of two liquids. In this paper, new controlling methods of mixing phenomena between two liquids are proposed, where a direct electric current and a stationary magnetic field are utilized. Vertical Lorentz force due to the interaction between the electric current and the magnetic field can modify the gravity force so that the dispersion relation of surface wave and the instability on the interface can be change to improve or develop the innovative processes(l,2).In case that a direct electric current is imposed on two liquid layers with a stationary magnetic field, Lorentz force of each layer becomes different due to the difference of electrical conductivity. If Lorentz force acting on the lower layer is stronger than that on the upper layer, resonance frequency of the wave motion on the interface due to the gravity can be shifted from the frequency of a outer disturbance to suppress the wave motion. And also, the lower layer can be scattered into the upper layer as liquid particles by an instability phenomenon."

Jan 1, 2000

Gas flow and heat transfer phenomena in two industrial-scale waste-heat boilers of the Outokumpu copper flash smelting process were analyzed with a commercial computational fluid-dynamics (CFD) package Phoenics. Various operating conditions were simulated for the first boiler and particularly for the second boiler. The gas flow pattern was compared qualitatively with the physical laboratory models, and the general flow pattern was consistent with the laboratory visualization. The heat transfer simulation was validated with, temperature measurements for both boilers, and good agreement was reached between the computed temperature profiles and the measured data. The computational results indicate that gas flow in both boilers is of three-dimensional and recirculating nature. The numerical tracer experiments indicate that some dead volume is present in both boilers, and the boiler modification reduced the dead volume from 38% to 15% under basic operating conditions. Radiative heat transfer accounts for 65-90% of the total 'heat transported in the radiation sections of both boilers under different operating conditions. The modified boiler is very efficient for cooling the off-gases at almost doubled volume flow rate. The CFD modeling proved to be a useful tool for numerical experiments and analysis of boiler performance for process: optimization.

Jan 1, 1998

By M. C. Ruiz

The leaching behavior of chalcopyrite concentrate in acidic CuC12-NaCI-O2 solutions was investigated. Experiments were conducted under continuos flow of oxygen at atmospheric pressures. The results indicated that among the variables temperature has the largest influence on the dissolution of chalcopyrite in this medium, and high copper extraction can only be obtained at temperatures near the boiling point of the solution. It was also found that the stirring speed did not influence appreciably the dissolution of chalcopyrite. An increase in the oxygen flow rate up to 0.1 1/min increased the copper extraction. The total chloride concentration affects the dissolution of chalcopyrite up to about 4 M. Copper extraction of 93 % was obtained in leaching chalcopyrite of size fraction -400 # Tyler at 105 OC in 2 hours.

Jan 1, 1997

By Robert Vidal

A model of the homogeneous chemistry and transport processes within the separator of a chrome-alum electrowinning cell is introduced, discussed, and compared to experiment. The influence of diffusion, electromigration, and convection are included; it is found that convection was the dominant mode of transport for the experimental conditions. Simulation results explain experimental observations concerning an apparent disappearance of dichromate ions produced at the cell anode. The relation between potential drop across the diaphragm and the current and fluid flow is also illustrated. The model is used to recommend future experimental and theoretical work.

Jan 1, 1994

By Jorge A. S. Tenorio, Girley F. Rodrigues, Joner O. Alves, Denise C. R. Espinosa

"Rock wools are mineral fibers composed of amorphous silicates, due to their thermo-acoustic characteristics this material has a broad consumer market in the construction, automotive, and electric-electronics industries. This work studied the recovery of wastes from ornamental rocks (granite and marble) as partial raw materials in the production of rock wools. Residues from granite and marble cuttings are industrial wastes with considerable production and limited applications. These wastes should be appropriately managed because when discharged in rivers or lakes can cause siltation, and also they can cause serious human health problems, such as silicosis. Samples of produced materials with thickness smaller than 500µm were characterized by chemical analyses, XRD, and DTA. Results showed that the rock wools produced using granite or marble wastes have important properties, especially the melting point. This process decreases the extraction of mineral resources and provides a profitable destination for the ornamental rock wastes.IntroductionThe ornamental rocks industry is a sector with large production of wastes. During the granite and marble extraction processes and specifically during the rocks cutting (see Figure 1), approximately 35 tons of powdered rock per month can be produced. These residues should be appropriately managed, because when discharged in rivers, lakes or watersheds, they can cause siltation. Also, these wastes can cause serious human health problems, such as silicosis [1].Currently, the granite and marble wastes are mainly used in civil construction to produce materials in the form of mortar, bricks and tiles. However, due the current produced volumes and the average growth of world production estimated at 6% per year, new applications for these wastes are necessary [2]."

Jan 1, 2011

By Florian Kongoli

The optimal operation of the blast furnace depends considerably on the properties of the sinter fed into the furnace. As a result, the optimization of the sintering processes has a direct effect on the overall effectiveness of the iron making processes. In order to produce a good sinter special care needs to be taken in order to assure it has a good permeability and reducibility and it is able to retain these properties for a certain time. If the sinter starts to melt down early in the upper part of the blast furnace, where its solid state reduction is essential, permeability decreases, the gas channels get blocked, reductibility diminishes and serious problems may also follow. Among the factors that influences the above mentioned sinter properties are the oxygen potential and fluxing components. Nevertheless, their effect on the phase relations during sintering and sinter reduction conditions has not yet entirely clarified and confusion exists in literature. This quantification becomes even more important today where many new minor components such as Al2O3 and MgO enter the sinter through raw materials. This work quantifies the effect of oxygen potential and fluxing components such as alumina and magnesia on the liquidus and phase relations of the sinter primary melts in the iron rich portion of CaO-FeO-Fe2O3-SiO2 system at sintering conditions. This is carried out by the means of new type of industrial diagrams in the form of Fe/CaO vs. SiO2 that can directly help the optimization of the sintering processes.

Jan 1, 2006

By R. R. Beebe

"Laboratory and pilot-scale tests are almost invariably required before metallurgical development can proceed. Difficulties with sampling, as well as with classical chemical and physical scaleups, are normally anticipated and relatively well-understood, but more subjective factors also come into play, including misunderstandings of the operating scheme chosen, wrong ""lessons"" learned from similar operations, failures to handle data appropriately, and even arbitrary intervention by management. The paper examines some of these subjective factors and suggests ways to guard against them. Several anecdotal case studies are used as examples, including when and where to heap leach or to mill specific types of gold ore.When the Romans first exploited the gold-rich gossans at Rio Tinto, they were guided by analyses and tests that delineated the ore deposits, identified the richer portions, and measured the gold recoveries achieved. There is little evidence, however, to suggest that test data were used to develop improved methods of metallurgical extraction. Indeed, it is likely that ores too difficult to treat were simply passed by, at least until improvements in full-scale operations could deal with them. For example, it is not difficult to imagine that an early metallurgist might test a tin ore by placing some in a fire; a smallscale emulation of the method actually used in practice."

Jan 1, 1997

By T. H. Eyde

Several hundred natural zeolite deposits occur in Tertiary and Cretaceous age formations of the western United States. Most of the large deposits are altered vitroclastic tuffs. Many of these deposits consist of a matrix of a high purity zeolite mineral or minerals in which fragments of unaltered rock are imbedded. These deposits represent an extensive resource of zeolite minerals which can be beneficiated to a consistently uniform, high quality product. The beneficiated natural zeolite products will possess many advantages over the selectively mined, unbeneficiated natural products currently being produced. These advantages will include: uniform particle size, high purity, consistent quality, high brightness, low iron content, high attrition resistence, uniform cation exchange and adsorption capacities, and low price.

Jan 1, 1981

By Roderick 1. L. Guthrie, Mei Li

"A mathematical model was developed to study the role of orifice shape in the detection of inclusions in LiMCA (Liquid Metal .cleanliness Analyzer) system. The fluid flow field within the ESZ was obtained by solving the Navier-Stokes equations. The trajectories of entrained particles were calculated using the equations for motion of particles. A numerical study of the effect of orifice shape on signal shape generated by inclusions passing through orifice showed that the signals in a parabolic orifice are gaussian in shape, while those in a cylindrical orifice are trapezoidal in shape. This signal shape difference needs to be taken into account when performing particle discrimination. Orifice shape influences also pass-through fraction of inclusions. Finally, a study of the orifice shape on critical conditioning currents suggested that as the polynominal coefficient of the parabolic orifice increases, the critical conditioning current, which is also the maximum operating current, decreases dramatically. These critical conditioning currents also increase as the fluid flow velocity within the ESZ increases. IntroductionThe presence of non-metallic inclusions in metals often leads to impaired mechanical properties such as a reduction in fatigue strength, and to processing problems such as tear-offs in deep drawing and increased breakage rates in wire drawing operations. Similarly, inclusions cause a variety of surface defects in rolled or extruded products.Prior to the development of the LiMCA system (1) at McGill University in the early 1980's, it was not possible to measure inclusions, in situ, in liquid metals. Compared with other techniques, such as sedimentation, filtration and metallography, which require considerable amounts of labor and time, the LiMCA method has the advantage of providing not only information on the volume concentration of inclusions, but also on the size distribution of inclusions immediately and quantitatively."

Jan 1, 2001

By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By Victor Stancovski, Uday Pal, Stephen C. Britten

"An in situ electrochemical technique for measuring the concentrations of easily dissociable oxides in slags at temperatures between 1200-1600°C is being developed. The technique utilizes a partially-stabilized-zirconia solid electrolyte (PSZ), which conducts oxygen ions, to separate a reference-gas compartment from the slag of interest. Three types of measurements are currently under investigation which yield different information concerning the slag phase and hence will be combined into a single amperometric device for monitoring the properties of easily dissociable slags.Type I utilizes an open-circuit-voltage measurement between the reference gas and the slag phase. Type II utilizes a potentiostat to apply a direct current potential step or sweep between the inner and outer compartments of the electrolyte, driving oxygen ions from the slag into a reference gas. With the use of open-circuit-reference electrodes, the resulting current-potential profile reveals the dissociation potential and concentration profile of dissociable oxides such as those of iron, manganese, and chromium. Information on the transport properties of the cations can also be generated from these measurements. Type III utilizes a potentiostat with reference electrodes to carefully electrolyze a known volume of slag by removing large quantities of oxygen ions from the slag to the reference gas. The coulombs of charge removed at different applied potentials can be used as a direct indication of the concentration of each dissociable oxide species present within the slag."

Jan 1, 1997

By D. M. Jones

In May 1999 the first campaign of the BHP San Manuel flash smelting furnace (FSF) will be concluded after having set world records for both campaign length and tonnage smelted for an Outokumpu copper flash smelting furnace. This paper reviews planned process and equipment modifications including: The installation of a new 36,000 mt concentrate storage facility; replacement of the existing dryer electrostatic precipitator with a baghouse; modification of the FSF dry charge bin and feed system to achieve mass flow and uniform feed to the concentrate burner; modifications to the FSF and its ancillary cooling systems; modifications to the waste heat boiler and offgas handling system to increase gas handling capacity and improve process efficiency;- and improvements to the FSF fugitive gas collection system. A brief review of the planning and execution of the scheduled 45 day shutdown is also given.

Jan 1, 1999

By A. J. Paul

Traditionally, 16"/50 caliber projectile shells have been fabricated from forged steel. The Naval Surface Warfare Center (NAVSWC) has determined that cost savings of approximately 60% (-$4.7M/year) as well as improved shell fragmentation can be achieved by casting these shells from austempered ductile iron. One of the technical concerns arising out of this material substitution is the role of the casting process in controlling the quality of the cast shells. Optimizing the process through proper orientation of the mold, placement of chills, superheat, etc., can minimize shrinkage porosity and, consequently, flaw size. For this purpose, the mold filling and subsequent solidification of the projectiles was simulated using a 3-D, fully transient, coupled fluid flow and heat transfer model based on finite differences. Several casting orientations were investigated and the casting parameters were varied to optimize the process and minimize casting defects. A comprehensive software tool, which was developed using state-of- the-art visualization techniques, has been used to analyze the process of casting. Emphasis is placed on the use of this visualization tool as an aid to the foundry engineer for process optimization.

Jan 1, 1992

Pyrometallmurgical reactors constitute a key processing component in the total primary and secondary resource cycle, being involved both in primary smelting, converting and extraction, as well as the reprocessing of scrap, from aluminum cans to end-of-life automobiles. To effectively control the overall resource cycle, one needs to take a systems modeling approach of the whole cycle, seeking to also understand the dynamic process behavior of the individual components of the cycle, and then especially the part that contributes most to the chemical conversion, namely the pyrometallurgical reactor. This paper highlights the role of pyrometallurgical thermodynamics, in the whole resource cycle and specifically places equilibrium thermochemistry in the context of process dynamics where large variable inventories are recycled or maintained within the system. This paper will therefore review the semi-empirical dynamic modeling tools, which are used to model complex systems with the specific goal of developing dynamic predictive models, which also include slag-alloy chemistry, towards controlling the recycling in a feed forward manner. To illustrate the primary processing side, high carbon ferrochrome will be presented as a brief case study. It also will show how the distributed nature of the chemistry of melts in the case of primary extraction, and secondary materials such as recycled end-of-life vehicles, have a significant impact on the process outcomes and model predictions. It is therefore argued that the fundamental thermodynamics and kinetics in metallurgical reactors playa final crucial role in modeling the closed material cycle, but only when it is used in conjunction with process systems theory based on reconciled data for parameter estimation and model calibration.

Jan 1, 2003

By Gabriel Plascencia

Copper was oxidized in the temperature range from 300 to 1000 °C under different pressures of oxygen, In the range from 300 to 500 °C, copper oxidizes following the logarithmic rate law; while in the range from 600 to 1000°C oxidation follows the parabolic rate law. Transition from logarithmic to parabolic growth occurs at about 525°C. X-ray diffraction was performed on oxide scales to account for the CuO/Cu2O ratio at different temperatures. Activation energies found in this work are in good agreement with reported values.

Jan 1, 2003

By Mitsuru Tanahashi

In order to develop an effective process for the production of a solar-grade silicon (SOG-Si) from metallurgical-grade one (MG-Si), the oxidation removal of boron from molten MG-Si was investigated at 1773 K by the following two CaO-saturated CaO-CaF2 flux treatment processes. I) Boron removal by flux addition onto the molten MG-Si followed by oxygen gas injection into the melt (Two-stage connecting process). II) II) Boron removal by simultaneous injection of flux powders and oxygen gas into the molten MG-Si (Simultaneous injection process). These processes can establish the special condition of both high basicity of the flux and the high oxygen partial pressure at the boron removal reaction sites. Through these processes, especially by the simultaneous injection process using a flux powder injection equipment, the boron content in MG-Si can be efficiently reduced. The obtained results clarified that both processes should be conducted for a time period as short as possible by using as much flux as possible. By repeating the simultaneous injection process for 60 s three times under the optimum operating conditions determined in the present study, the boron content in MG-Si can be reduced from 14 to 4.7 mass ppm.

Jan 1, 2003

By Krzyszof Borowiec

With the aim of determining the thermodynamic conditions for sulfation of impurity elements, in particular magnesium, in titaniferous slags the equilibrium gas composition for the sulfation reaction: MO + so2 + 1/2 02 = MS04 has been studied by an EMF technique with a solid zro2 + Cao electrolyte. Here M denotes the impurity elements: Mg, Ca and Mn, and the following _oxide systems have been studied: Ti02-MgO-Fe2 o 3 , Ti02-MnO-Mn2 o 3 , and Ti02 -CaO-Si02 , all in the . temperature range 700-1000ºc. Reproducible EMF values were obtained by adding small amounts of -Na2so4 to the oxide-sulfate mixture. From the observed results the Gibbs energy of formation of the phases Mg 2Ti04 , MgTi03 , MgTi 2o 5 , MnTi03 , CaTi03 , and CaTiSio5 , as well as the activity of MgTi05 in the solid solution with Fe2Ti05 have been calculated. The results show that, from a thermodynamic viewpoint, sulfation of these impurities in titaniferous stags i:s favorable- at around and below 800ºC.

Jan 1, 1985