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By S. P. Rivers

The stainless steel industry re1ies on nitric-hydrofluoric acid (HNO,/HF) pickling solutions to remove surface contaminants and maintain the corrosion resistance of the steel. More stringent environmental guide1ines are expected to be placed on the disposal of these solutions which could significantly increase processing costs. The U.S. Bureau of Mines has been conducting research to develop a process for recycling depleted pickling solutions, thus reducing the quantity of by product acids generated. Research has shown that F- can be liberated from the predominant iron fluoride species (FeF,') by using oxalic acid in an electrodialysis cell. Ion selective membranes allow dissolved metals in the depleted solution to be replaced with hydronium ions by metathesis, thereby regenerating the HF. The regenerated HN03/HF is then retained in the pick1ing solution. This paper reports on the research effort at the U.S. Bureau of Mines Rolla Research Center to apply electrodialytic recycling to HN03/HF pickling solutions.

Jan 1, 1993

The merging of flash smelting with spray converting in one single furnace is proposed as a continuous copper making process. The proposed process is expected to produce blister copper, clean slag and gas with high sulfur dioxide concentration. Some high grade matte is an intermediate product recycled within the proposed furnace, spray-atomized and converted. The thermodynamic equilibria of the simultaneous oxidations which take place during copper smelting and converting are discussed in order to establish the gradient of oxygen potential along the furnace required for smooth operation. The proposed process is a dynamic system designed to reach equilibrium only close to the slag skimming end of the furnace. The process feasibility is based on the predesigned significant difference between the rates of converting reactions in a finely dispersed system and the rates of deconverting reactions between immiscible liquid phases of restricted interface area. The converting of small stationary droplets of matte, in a silica saturated system, was studied in the laboratory for extremely short oxidation times (10 to 120 seconds). These experiments led to some interesting observations on reaction mechanisms and kinetic trends. The droplet size and the matte grade affected very strongly the oxidation rate and the proportion of the different products obtained.

Jan 1, 1976

By Robert R. Grinstead

Two new ion exchange resins have been developed, which selectively absorb copper and nickel in preference to ferric iron from dilute sulfuric acid solutions of pH 1-3. The first absorbs copper and not nickel and can be readily eluted with 1-2N sulfuric acid. This resin is well adapted to the processing of copper leach liquors, including relatively low grade liquors obtained from dump leaching. The second resin absorbs nickel as well as copper in the same pH region, but only the nickel is eluted with 1-2N sulfuric acid. Elution of the copper requires much stronger (ca. ION) acid, altho both species are readily eluted with dilute (ca. lN) ammonium hydroxide. This resin, which should be useful in processing of certain types of copper-bearing solutions, may also be suitable for treating acidic nickel leach solutions of laterites and other non-sulfide ores.

Jan 1, 1976

By Yuhsuke Mizukami

Crude high Cr containing steel such as tool steel, heat-resistant steel or stainless steel is produced by dissolution of high carbon ferro-chromium into molten crude steel. In the refining process, decarburization is performed at the first stage, and deoxidation is followed in the next stage. Therefore, the equilibrium relation between dissolved Cr and 0 in molten Fe-Cr alloy after decarburization is very important when yield of deoxidizer is considered for the ovemll control and optimization of the process. It is well known that the yield of deoxidizer does strongly depend on the kinds of refractories of furnace in the secondary refining process. In the present work, the equilibrium relation between dissolved Cr and O in molten Fe-Cr alloy has been measured in a Cr2O3, MgO or Al2O3 crucible at steelmaking temperature. O contents at given Fe-Cr components have been lower in order of Cr2O3, Al2O3 and MgO crucible. The present results have been discussed based on the activities of the constituents in pure solid Cr2O3, and FeO-Cr2O3, MgO Cr2O3 and (AI,Cr)2O3 solid solutions.

Jan 1, 2003

By Józef Czemecki

Polish copper concentrates are characterized by high levels of impurities, particularly Pb and As. Two technologies are being used for copper concentrate smelting at KGHM Polska Meidz S.A., namely the shaft furnace process (Legnica Copper Smelter, Glogów I Copper Smelter) and a single-stage process for direct to blister concentrate smelting in a flash furnace (Glogów II Copper Smelter). Both technologies are used at different physical and chemical conditions which results, in different impurities behavior. The paper presents flow sheets for copper production in a plant using the shaft furnace process and in another in which a single stage flash process is used. The metals distribution in particular semi-products is given as well as a method for elimination of impurities from the copper production cycle. Methods are also discussed for alloy and matte converting and copper refining to obtain low Pb and As concentrations in anode copper (0.3% Pb and 1500 ppm As maximum) that are being used in the KGHM Polska Meidz plants. Useful co-operation between the plants using different technologies, aimed at the limiting the effect of undesired impurities on the quality of blister copper produced, is also described.

Jan 1, 1998

By Zhang Hengzhong

Based on thermodynamics of surfaces and a proposed two-dimensional state equation for surfaces, the relationship between the surface tension (Y) of a solution and the activity (a1) of its component (i) was derived: (1/Y)r2-.¬E (ai/Yl) The derived equation was verified with reported experimental data of water-alcohol systems and water-acetone system, the calculated results showed astonishing coincidence with experimental. Applications of the equation to the five matte systems Cu2S-FeS, Ni3S2-FeS, FeS-PbS, Cu2S-PbS and FeS-Cu22S-PbS also demonstrated that at given matte compositions the calculated surface tensions agreed with experimental fairy well.

Jan 1, 1993

By L. E. Murr

Preliminary studies of bacterial attachment to MoSp (molybdenite) have indicated a low correlation between dislocation density in the (0001) basal plane and the density of attached microbes. In the present investigation, poly- crystalline thin sections of CuFeSp (chalcopyrite) have been ion-etched or carefully comminuted to electron transparency and observed in the transmission electron microscope. The thinned test sections were then immersed in a culture solution in which bacterial attachment occurred. The attached bacteria were biologically stained in a uranyl acetate solution and the entire thin CuFeSp sections or tiny particles containing thin, electron transparent edges with bacteria attached were observed in the transmission electron microscope, allowing the coincidence of bacteria and their density to be directly observed in relation to lattice dislocations and crystallographic orientations of the exposed surfaces. This technique has the advantage of exposing crystallographic orientations where dislocation lines intersect the free mineral surface, and the emergence sites of dislocations could in principle be directly investigated as a possible preferential attachment site for bacteria. Bacteria morphologies were also extensively observed in the scanning electron microscope. The implications of the results are that although a strong correlation between dislocation density and distribution and bacterial attachment, density, and distribution has not been established, systematic multiplication of dislocation densities in crystalline mineral particles to be leached could enhance leaching rates by increasing the reaction rates as well as the density of attached bacteria at crystalline, metal-rich phases. Techniques for dislocation production in mineral and ore bodies and the particular implications in chalcopyrite leaching are discussed in relation to in-situ leaching where comminution is attained by explosives and the generation of strong shock waves in an ore body. The present study demonstrates the use of microanalytical and microscopic techniques in the investigation of fundamental microstructural phenomena in hydrometallurgical processes.

Jan 1, 1976

The present work is mainly focused on developing intermetallic inert anodes for aluminum electrolysis. The anode alloy based on Al-Ti-Cu system was prepared by casting, followed by the application of a protective coating. Behaviour of corrosion and the passivation under anodic condition was characterized using the electrochemical and microscopic techniques. The results obtained clearly demonstrate that the oxide coating can provide good corrosion resistance via surface passivation of alloy anodes, rendering them inert in cryolite melt.

Jan 1, 2006

By Alan James Parker

Chalcopyrite can be converted to pure copper by the following five steps. An exothermic sulfation roast of chalcopyrite; leaching of cupric sulfate from the calcine with dilute acid; precipitation of Chevreul's salt and or other copper sulfites with ammonium sulfite or precipitation of crude copper by autoclaving ammonium sulfite and cupric sulfate at 150°C; dissolution of Chevreul's salt, or the crude copper, as cuprous sulfate, using acidic cupric sulfate in an acetonitrile-water solution as oxidant; precipitation of pure copper by thermal disproportionation of the cuprous sulfate solution. Acetonitrile and acidic cupric sulfate solution recycle. Advantages over conventional processes include lower cost, lower energy consumption as waste heat, sulfur removal as ammonium sulfate or gypsum, rather than as sulfur dioxide and rapid throughput. The net reaction is: 2 CuFeS2 + 4H20 + 15/2 02 + 8 NH3?2Cu + 4 (NR4)2 SO4 + Fe2O3

Jan 1, 1976

By Keiji Okumura, Jiayi Shan, Jian Yang, Masamichi Sano

"A new method of deoxidation and desulfurization of molten iron with magnesium vapor has been developed. An immersion tube, which was filled with pellets of the mixture of magnesia and carbon powders, was put into the molten iron. Magnesium vapor produced by carbothermic reduction of magnesia inside the tube was injected directly into the molten iron with argon carrier gas. The effects of temperature and carrier gas flow rate on deoxidation and desulfurization were investigated. A mathematical model of the reactions was developed. The rates of deoxidation and desulfurization were controlled by mass transfers of magnesium vapor in the gas-phase and oxygen and sulfur in the liquid-phase. This method may offer high efficiency for magnesium deoxidation and desulfurization of molten iron.IntroductionMagnesium is a strong refining agent in steel-making processes1 • At steelmaking temperatures, magnesium has a very low solubility in liquid iron, and a very high vapour pressure2 • Deoxidation and desulfurization with magnesium take place essentially through the interaction of magnesium vapor with oxygen and sulfur dissolved in molten iron, and magnesium can change chemical composition of nonmetallic inclusions3 • However, addition of magnesium to the steel bath is dangerous and does not give high efficiency in the refining process4 • Furthermore, as a refining agent, the price of magnesium is higher than aluminium and CaO fluxes. In the present study, a new method of the deoxidation and desulfurization of molten iron was developed using magnesium vapour in-situ produced by carbothermic reduction of magnesium oxide. Pellets made of mixture of magnesia and carbon powders were charged into an immersion tube, which was made of alumina or graphite. The magnesium vapor was injected directly into the melt. The effects of pellet mass, experimental temperature and carrier gas flow rate were studied on the refining rate. A mathematical model of the refining reaction was proposed on the basis of the experimental results."

Jan 1, 2000

By Sven Eck, Andreas Ludwig, Menghuai Wu

"Phase separation is a frequently occurring phenomenon during solidification accompanied by melt convection, sedimentation or, in the case of two unmixable liquids, a Marangoni driven motion. In order to describe these phase separation phenomena a two-phase volume-averaging model was employed for globular equiaxed solidification of binary alloys and decomposition and solidification of hypermonotectic alloys. The model considers nucleation and growth of equiaxed grains or second phase droplets, motion and sedimentation of grains or droplets, feeding flow and solute transport by diffusion and convection. It allows the prediction of macro segregations and the distributions of grain size or droplet size. Evaluations were made by comparing the numerical predictions with experimental results. For example it is shown that the numerically predicted grain size distribution in a plate casting (Al-4wt%Cu) agrees reasonably well with the experimental analyses.IntroductionModeling of metallurgical processes is a rapidly expanding field and the research activities in the last decades cover a wide range of areas including melt pre-treatment, solidification and subsequent manufacturing routes. Among those activities solidification stands in the central position, because the primary structure of the materials, and even many defects such as porosity, (macro or micro) segregation and inclusions form during solidification. Those primarily formed structures or defects once existing are difficult to be removed or modified by the subsequent material processing.Solidification is a multi-disciplinary field involving thermodynamics, fluid dynamics and solid mechanics, heat and mass transfer, and other disciplinesr1 -31• One of the most challenging problems in solidification modeling is the complex interactions between physical phenomena occurring on different length scales ranging from atomic rearrangement over single crystal-melt interactions to heat extraction, momentum and species transport at the system level. Modeling an industry process on atomic scale is umealistic, even on grain scale (e.g. phase field method) it would need another 40 years to be able to model the exact grain morphology in a casting space envelope of 10x10x10 cm3 [ 4]. Therefore, the realistic models for industry process are based on the solution of the macro transport equations (mass, momentum, enthalpy and species) on system scale. The microscopic phenomena such as thermodynamics, nucleation law, crystal growth kinetics and interactions at the liquid-solid interface are considered with simplified models, which are coupled with the macroscopic transport equations."

Jan 1, 2004

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, PSo, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of O2 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By G. S. Rao

Levitated drops of Fe-18%Cr-2%C were reacted with oxygen-argon mixtures to study the reactions that occur in the AOD process, where the gases are injected into the melt and form bubbles. In the laboratory an argon-oxygen pulse, followed by pure argon, was flowed past the levitated drop to simulate the transient conditions in the gas phase as the bubbles rise in the melt. Oxide layers formed on the drops immediately when they came into contact with gas pulses containing 75% or more oxygen. Once the oxygen flow had ceased, the oxides reacted with the carbon in the drops to form CO gas and eventually disappeared. The de-carburization reaction occurred without oxide formation when the gas contained 50% oxygen or less. Melts that were sampled after EAF tapping, ready to be charged into the AOD, showed a higher tendency to oxide formation and consequent carbon boil than pure ternary Fe-18%Cr-2%C alloys made in the laboratory. The actual steel samples contained significant impurities, such as 0.25% Si and 0.56% Mn. A similar effect of oxide-forming impurities had been observed previously with binary Fe-C alloys. Movies were taken of the oxide formation and decomposition, and the results will be presented, along with data on the experimental conditions, including temperature and oxide compositions. The results are important because they give an insight into the reaction mechanisms in the AOD, which must be understood in order to improve and model the process.

Jan 1, 2006

By Ruiqing Li

It is possible to purify some liquid metals by exploiting the difference between the vapour pressure of the bulk metal and the minor constituents or impurities. The rates of purification can be improved by carrying out the process under reduced pressure, that is, so called, vacuum. Some commercial examples of vacuum refining are the purification of molten tin to eliminate trace amounts of lead and the refining of cobalt, also to remove lead. The objective of this paper is to review the basic theory behind vacuum refining technology in order to show how the feasibility of vacuum refining can be determined simply for a particular system by evaluating Olette's Volatility Refining Criteriont.

Jan 1, 1991

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By Paul L. Wichlacz

A mathematical model of growth and ferrous iron oxidation for attached bacteria was applied to rotating biological contactor (RBC) units treating acidic mine drainage. The model describes attached bacterial growth as a saturation function, where the rate of substrate utilization is determined by a maximum substrate oxidation rate constant, a half saturation constant, and the concentration of substrate within the RBC. The maximum oxidation rate constant was proportional to flow rate and the substrate concentration in the reactor varied with influent substrate concentration. The model was tested at three separate sites and with three different size RBC units. The ability of the model to predict the rate of iron oxidation under all test conditions was significant. The accuracy of the model was found to be affected by unit size and vary with specific test site.

Jan 1, 1985

By Robert E. (Bob) Brown

Magnesium was discovered by Davy in 1808. The production processes as they exist are not economically competitive with aluminum The electrolytic magnesium process is divided into two steps; one to make the MgCh feed and the other to apply large amounts of electric current to dissociate the feed into magnesium (450 g) and chlorine (1200 g). The production of fuJIy anhydrous, pure cell feed is a major problem Recently, there has been a growth of thermal processes, mainly the Pidgeon silicothermic production process using FeSi to reduce dolomite in horizontal retorts. Pechiney has a large vertical electrical furnace process that also uses FeSi to reduce calcined dolomite in a molten bath containing alumina. Work is proceeding to develop new or modified processes that will greatly improve magnesium production. The present methods and the research and R&D will be reviewed in this paper.

Jan 1, 2001

By Shantaliu S. Shevade, Muhammad M. Rahman

"This paper presents a systematic analysis of fluid flow and heat transfer processes during the magnetic heating of the substrate material. Heat is generated in the substrate material when a magnetic field is imposed due to change in orientation of the molecules. As a result, the substrate temperature rises. The i;tudy considered microchannels with rectangular and square cross section with heat generation in the substrate due to imposed magnetic field. The results computed were for Gadolinium substrate and water as the working fluid. The purpose of this study is to explore the transient heat transfer coefficient when the fluid is circulated through the substrate via microchannels. Equations governing the conservation of mass, momentum, and energy were solved in the fluid region. In the solid region, heat conduction was solved. From the simulation results, plots of Nusselt number and heat transfer coefficient were obtained over the length of the channel. A thorough investigation for velocity and temperature distributions was performed by varying channel aspect ratio, Reynolds number, and heat generation rate in the channel. It was found that the peripheral average heat transfer coefficient and Nusselt number is larger near the entrance and decreases downstream because of the development of the thermal boundary layer. With the increase in Reynolds number, the outlet temperature decreased and the average heat transfer coefficient increased.IntroductionMagnetocaloric effect (MCE) is the heating or cooling of the magnetic materials due to varying magnetic field. The effect was originally discovered by Warburg. Magnetocaloric materials store heat energy in the way the atoms vibrate and in the way electrons spin within each atom. More heat energy increases the vibrations and also makes the spins more random. When a strong magnetic field is applied to a magnetic material, the magnetic moments of its atoms become aligned making the system more ordered. The more ordered material has lower entropy and compensates for the loss by heating up. When the magnetic field is removed, the magnetic moments return to their random directions, entropy increases and the material cools. Gadolinium is a magnetic material that exhibits high temperature rise during adiabatic magnetization around its transition temperature of 295 K. It has been experimentally observed that adiabatic temperature rise increases with magnetic field strength and can be as high 20 K when a magnetic field of IO T is applied. Thus magnetic field, when applied to a microchannel heat exchanger, causes temperature change in the magnetic material. The fluid flowing through the channel gets cooled or heated due to this adiabatic temperature change."

Jan 1, 2004

By Jan Petter Maehlen

Solid H-absorbing materials are in focus of ongoing R&D to offer viable solutions for the hydrogen storage and supply systems aimed on use of hydrogen as energy carrier for automotive transportation. Low operating pressures, combined with high gravimetric and volumetric efficiencies, together with fast kinetics of hydrogen release at ambient temperatures (providing conditions for a low energy loss due to decomposition), are the most important features of the ?ideal? H storage material. Hydrides of the light elements are the only possible candidates to build systems with an overall efficiency similar to those accommodating liquid or compressed (700 bar) hydrogen. One promising material from this point of view is aluminium trihydride, alane AlH3 with a gravimetric storage capacity of 10 wt.% H. This work was focused on studies of the crystal structure and thermal decomposition of alane by application of powder synchrotron X-Ray diffraction.

Jan 1, 2006

By James A. Voigt

"The efficient separation of metal species from aqueous streams by precipitation techniques requires a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems. The effects of solution chemistry, precipitator design, and solvent choice are considered.IntroductionThe application of precipitation technologies to the separation of metals from solution is widely used. Regardless of its application, be it in such diverse areas as the preparation of metal oxide powders for use in commercial products or as a unit operation in the removal of trace metals during wastewater clean up, the fundamental processes involved are the same. These processes include: nucleation from solution, either homogeneous or heterogeneous; growth from solution with chemical reaction either in solution or at the precipitate/solution interface; growth by particle agglomeration; and particle break-up by collisional or shear forces. The effectiveness of the operation and the properties of the precipitate formed, or ""quality"" of the product, are determined by the competing kinetics of the different processes. The kinetics of the processes, in tum, are determined by system-specific solution chemistries and the conditions used to carry out the precipitation operation. For example, generally, when system conditions are such that the supersaturation driving force for precipitation is very high, growth species normally do not have the time to organize themselves with a high degree of crystallographic order and the precipitate is amorphous. In this case nucleation rates are invariably extremely high and the primary mechanism for growth is the agglomeration of nuclei. Conversely, when the supersaturation levels for the same system are reduced, the kinetics of the nucleation and growth processes also are greatly reduced, and a crystalline precipitate can be formed, since the growth species have time to order on particle surfaces."

Jan 1, 1996