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By Philip L. Sibrell

A new process utilizing pulsed fluidized limestone beds was tested for the remediation of acid mine drainage at the Friendship Hill National Historic Site, in southwestern Pennsylvania. A 230 liter-per-minute treatment system was constructed and operated over a fourteen-month period from June 2000 through September 2001. Over this period of time, 50,000 metric tons of limestone were used to treat 50 million liters of water. The influent water pH was 2.5 and acidity was 1000 mg/L as CaCO3. Despite the high potential for armoring at the site, effluent pH during normal plant operation ranged from 5.7 to 7.8 and averaged 6.8. As a result of the high influent acidity, sufficient CO2 was generated and recycled to provide a net alkaline discharge with about 50 mg/L as CaCO3 alkalinity. Additions of commercial CO2 increased effluent alkalinity to as high as 300 mg/L, and could be a useful process management tool for transient high flows or acidities. Metal removal rates were 95% for aluminum (60 mg/L in influent), 50 to 90% for iron (Fe), depending on the ratio of ferrous to ferric iron, which varied seasonally (200 mg/L in influent), and <10% of manganese (Mn) (10 mg/L in influent). Ferrous iron and Mn removal was incomplete because of the high pH required for precipitation of these species. Iron removal could be improved by increased aeration following neutralization, and Mn removal could be effected by a post treatment passive settling/oxidation pond. Metal hydroxide sludges were settled in settling tanks, and then hauled from the site for aesthetic purposes. Over 450 metric tons of sludge were removed from the water over the life of the project. The dried sludge was tested by the Toxicity Characteristics Leaching Protocol (TCLP) and was found to be non-hazardous. Treatment costs were $43,000 per year and $1.08 per m3, but could be decreased to $22,000 and $0.51 per m3 by decreasing labor use and by on-site sludge handling. These results confirm the utility of the new process in treatment of acid impaired waters that were previously not amenable to low cost limestone treatment.

Jan 1, 2003

By Oleg B. Girin, Yuliya O. Proshenko

"Several approaches to electrolytic synthesis of new types of composite coatings with improved properties were devised using the authors' findings on development of texture, substructure and structural state in metal electrocrystallization. Addressed are texturally composite coatings having improved resistance to wear and corrosion; substructurally composite coatings having improved hardness and corrosion resistance; phase-change constitutionally composite coatings having improved corrosion resistance, reflectance, hardness and resistance to wear; structure-change constitutionally composite coatings having improved electric and magnetic properties; restricted-substructure composite coatings having improved resistance to abrasive-impact wear; and modified-substructure composite coatings having improved strength and plasticity.IntroductionIn recent years, some trends in the formation behavior of crystal texture, crystal substructure and structural state of electroplates were revealed and effects of texture, substructure and structural type on electroplate properties were discovered (1-3). Our interest was in using these findings and effects to develop some ways of synthesizing new types of composite electrolyte coatings having enhanced properties."

Jan 1, 1998

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 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

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

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 &apos;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 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 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 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 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

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 Robert M. Leary

The Kennecott Utah Copper smelter operates two Outokumpu flash furnaces: a smelting furnace for production of high-grade matte and a converting furnace for production of blister copper. Flash furnaces typically possess several characteristic features that must be considered in process control development such as long lag times associated with settler volume, non-linear input and output responses, large process gains, and unmeasured disturbances. Additionally, the Kennecott smelter possesses certain unique characteristics which must be considered such as single mine concentrate source, limited concentrate blending capacity, and feed preparation facilities that inevitably cause significant lags between furnace control parameters and manipulated set points. In order to improve furnace control and on-line time, a process control system was developed to address these issues. The feed forward control module provides predictive control and operates in response to furnace feed input changes. The feed back control module provides responsive control and is based on furnace output deviations. To provide regular feed back information to the control room supervisors, new sampling methods were developed which provide the operators with molten metal and bulk material samples at regular intervals to provide information for control. The control system was implemented on the Flash Converting Furnace in May 1999 and on the Flash Smelting Furnace in August 1999.

Jan 1, 2000

By Kouji Mimura, Tamas Kekesi, Yongfu Zhu, Masahito Uchikoshi, Minoru Isshiki

"The formation and anion exchange sorption of chloro complex ions can offer a great potential to be utilized for the separation and purification of metals in aqueous solutions. Available stability data were primarily used to estimate the predominance of chloro complex species, indicating the feasibility of such separations. Anion-exchange sorption functions, describing the equilibrium distribution of a number of important elements have been determined by the batch equilibrating method in the practical HC1 concentration range. Various oxidation states were stabilized by the addition of appropriate agents. Tendencies in oxidation, complex formation and anion exchange sorption were confirmed by spectrophotometric investigations. Based on the fundamental results, anion exchange processes have been developed for the purification of iron, cobalt, copper and zinc. The efficiency of separation was assessed and the procedure optimized by the analysis of experimental elution curves. Results have demonstrated that by properly controlling the oxidation states and HC1 concentrations, practically all the impurities can be eliminated. Computer programs have been developed to estimate complex formation and redox equilibria, to screen and correct analytical data, to determine distribution coefficients and to evaluate efficiencies of separation.IntroductionBase transition metals have long been used as the staple materials in various fields of industry. In general, there has been an increasing tendency in purity requirements but recent advances have created a rapidly increasing demand for ultra-high purity metals. To give a few examples, ultra high purity copper can be used as bonding wire and interconnection in integrated circuits, or as material for superconductor stabilizing, high-field magnets, beside its use in cryogenics and ultra high vacuum technology [1]. Iron holds promises as a constituent element in the ß-FeSi2 material to be applied in new opto-electronic devices [2] and it is currently used, together with chromium and manganese, in the production of special magneto-optical materials for digital recording. The use of ultra high purity manganese and chromium in semiconductor technology is evolving. Although not considered a transition metal, zinc is also treated here because of the major significance in compound ZnSe semiconductors [3], and the possibility to purify it by the anion exchange method."

Jan 1, 2000

By Milton Manrique

The thermal decomposition of ilmenite concentrates in a non-transferred arc; thermal plasma flow reactor was investigated. The plasma torch was operated using argon-helium and argon-nitrogen mixtures as plasma gases. The effect of power, feed rate and particle size was studied. Products were characterized by XRD, SEM, TEM and ICP techniques. Free energy minimization plots were used to predict the thermodynamic behavior of the system under different operating conditions. The results of this investigation showed a significant segregation process where titanium-rich products are collected in the reactor, while iron-rich products are collected in the quenching box and filter. The average size of the product is in the sub- micron range. Titanium nitride was formed and condensed in the reactor zone when using an argon-nitrogen mixture as the plasma gas.

Jan 1, 1998

By Dirk Verhulst

The Altair process employs digestion of ilmenite ore in concentrated hydrochloric acid, solvent extraction to concentrate Ti in a purified stream and spray hydrolysis to produce a TiO2 hydrate, followed by final calcining and milling. HCl gas is regenerated by pressure-swing distillation and reinjected in the leaching solution. All chloride streams are recycled. Chromium compounds generally remain in the residue. Solvent extraction provides flexibility for the removal of naturally occurring radioactive elements (NORMs) present in some ilmenites. The process was previously tested at a 5 t/day feed scale. Recent work at pilot scale (40 liter reactor) led to further improvements. Recovery of Ti in solution is now at least 90% with ilmenite ores, while crystallization at lower temperature lowers the amount of Fe in solution to about 5 g/l and improves solvent extraction, which is now conducted in columns. Higher Ti and lower Fe concentrations in the SX eluate improve the economics. A new formula for pigment production via spray hydrolysis produces a pigmentary base with a narrow particle size distribution.

Jan 1, 2003

By S. M. Copley, M. Yankova, E. Y. Yankov, J. A. Todd

"Nanophased coupled growth structures, with spacings of -10 nm, have been observed in banded microstructures produced by laser melting hypoeutectic Ag-Cu alloys. These coupled growth structures comprised a Cu-rich phase of width - 1 nm and a Ag-rich phase of width - 9 nm. In this paper, microstructural observations of nanophased coupled growth structures in hypo eutectic AgCu alloys are presented. Laser beam velocities for the transition from banded to microsegregation free microstructures are modelled and compared with experimental values. Models are presented to show that, at a critical undercooling, initial growth of a Ag-rich, metastable, extended solid solution is rapid but slows to a halt as copper is partitioned into the liquid at the solid/liquid interface. Following nucleation, the coupled growth structure then grows until the partitioned copper is consumed, at which point growth of the Ag-rich solid solution is again accelerated. This cycle then repeats resulting in banded microstructures comprised of 750 nm of the Ag-rich extended, metastable solid solution, followed by 250 nm of the coupled growth structure.1. Structural Studies of Laser Melted and Resolidified TrailsPresented here are observations of laser melted and resolidified trails in Ag-Cu alloys obtained at beam velocities ranging from 0.7 to 34 cm S·I. When the laser beam is scanned along the surface (positive x-direction) with a velocity Vb a melt pool with the shape given in Fig. 1a moves with the beam. The isotherms move with the velocity, Vi,. = Vb cos.p. Calculations employing the thermal analysis of Kou, Hsu and Mehrabian [1] for the beam velocities of this investigation and for the thermal properties of AgCu alloys, indicated that, .p, the angle between the isotherm velocity and beam velocity should be small at the surface where microstructural studies were made. This prediction was supported by observations of trail cross-sections. Based on these observations, and the calculations which include latent heat effects, the isotherm velocity for observations near the surface in our investigation was taken to be 27 cm S-I."

Jan 1, 1994