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By Adam Powell, Soobhankar Pati

"Solid Oxide Membrane (SOM) Electrolysis is a new energy-efficient zero-emissions process for producing high-purity magnesium and high-purity oxygen directly from industrial-grade MgO. SOM Recycling combines SOM electrolysis with electrorefining, continuously and efficiently producing high-purity magnesium from low-purity partially oxidized scrap. In both processes, electrolysis and/or electrorefining take place in the crucible, where raw material is continuously fed into the molten salt electrolyte, producing magnesium vapor at the cathode and oxygen at the inert anode inside the SOM. This paper describes a three-dimensional multi-physics finite-element model of ionic current, fluid flow driven by argon bubbling and thermal buoyancy, and heat and mass transport in the crucible. The model predicts the effects of stirring on the anode boundary layer and its time scale of formation, and the effect of natural convection at the outer wall. MOxST has developed this model as a tool for scale-up design of these closely-related processes.IntroductionSolid Oxide Membrane (SOM) Electrolysis is a variation on the Hall-Héroult process for molten salt electrolysis of oxides which promises to solve many of the problems of its predecessors. Magnesium in particular is both soluble in molten salts and highly reactive, such that it migrates to the anode and reacts with the oxygen or C02 anode product, reducing current efficiency to as low as 10-20%. But a zirconia solid electrolyte between the molten salt and anode blocks this reaction, boosting current efficiency to at least 90%. Separating the anode from the molten salt also opens up anode material selection to liquid metals and SOFC cathode materials such as Lai.xSrxMn03 (LSM) and YCr03. And zirconia's selectivity makes the oxygen by-product very pure."

Jan 1, 2012

By G. H. Khoe

Although some hydrometallurgical process liquors contain significant amounts of ferrous and arsenate ions, no reliable thermochemical data for the aqueous complexes and the solubility of the ferrous arsenate precipitate are available. The complexation of iron(11) with arsenate has been investigated using the potentiomemc titration method. The results indicated that virtually no complexation of iron(@ with arsenate has been observed. This is in contrast to the significant complexing reported for iron(1n) with arsenate. The solubility product of the precipitate was calculated using the concentrations of appropriate arsenate species pertaining to the observed precipitation pH's. The fit of the observed precipitation points on the solubility curve of the computed stability diagram was used to assess the appropriateness of the equilibrium model.

Jan 1, 1991

By Larry M. Southwick

Pneumatic converting (Bessemerizing) of iron revolutionized the steel industry. Bessemerizing of copper (conversion of copper sulfide matte to copper metal) was proposed at almost the same time, but it was slow in being accepted. The differences between iron and copper converting were great and technical problems were substantial. It took 25 years for the process to become viable and another 25 years before a truly economical solution was found. A major economical and productivity problem was the short life for converter refractory linings. The first converters had acid (silica) linings, which were quickly consumed since silica was a flux for the process. Converters had to be relined at least once per day, a laboriously expensive manual process with only the most rudimentary mechanical aids available to assist. The industry was revolutionized almost overnight when finally a viable basic (magnesite) lining was developed. This lasted 100's of days versus less than one, leading to converters that were easier to operate and which handled larger charges. This change occurred after W.H. Peirce and E.A.C. Smith, with support from the Guggenheim interests, successfully operated a basic lined converter in a copper refinery in Baltimore. While Peirce and Smith are generally given credit for the development and explosive acceptance of this idea, a Pittsburgh industrialist, Ralph M. Baggaley, working in an independent smelter in Butte, Montana, successfully built and operated a basic lined converter four years before they did. In fact, the early support for Peirce and Smith likely occurred because Guggenheim's staff were encouraged after thoroughly examining Baggaley on his earlier successes. The questions of technology primacy between Baggaley and Peirce/Smith are ironically similar to those between Wm. Kelly and Bessemer in converting iron to steel. This paper will review what Baggaley (and other early researchers) accomplished, examine why he (or they) did not receive credit equal to Peirce and Smith and explore what his (their) place should be in the development of successful basic linings. More suspects than a Victorian Whodunit.

Jan 1, 1999

By A. Elizabet Serna

The weak acid is a by product obtained in a pre-treatment of gases from a copper smelter prior to sulfuric acid manufacture and the main components of this weak acid are: sulfuric acid. copper, arsenic. antimony, bismuth and iron. Usually, this effluent is neutralized with lime and the solid residues are stored in a landfill as a hazardous waste. This work was directed at determining the optimal conditions to recover copper from weak acid using a cementation process before the neutralization of the effluent. The variables investigated are: Effluent temperature, iron scrap amount and acid concentration versus reaction time. The results of these experiments show that the cementation process of copper and the co-cementation of impurities such as arsenic, antimony and bismuth were in accord with the theory of the electrode potentials.

Jan 1, 1996

By Dieter Offenthaler

Catalysts used in petroleum industry often contain valuable amounts of PGMs. The typical recycling route for those materials is the pyrometallurgical one, but this treatment way offers limited flexibility with respect to small charge weights. A new process, combining a pyrometallurgical pre-treatment step of the ceramic carriers with a hydrometallurgical leaching procedure overcomes this disadvantage. It not only allows the economical treatment of even very small charge weights, but also gives the possibility to maximize the PGM yield by individually adapting the process to the different charge materials. Due to an ingenious process design, where all leaching agents and effluents are recycled in a closed loop and therefore no waste waters leave the process, process operation becomes very economical. However, the temperature-time-regime in the pyrometallurgical pre-treatment step is of major importance for the success of the whole process. Therefore various investigations have been done to identify how the different process variables in the pyrometallurgical pre-treatment influence the subsequent leaching procedure. It turned out, that the adjustment of the correct phase-modification in the ceramic carrier materials during the pyrometallurgical treatment is the key factor of this process step. Although it is a troublesome issue to exactly adjust the correct phase modifications, it is the prerequisite to take advantage of the benefits of this new process concept.

Jan 1, 2006

By D. N. Collins

A sampling program was conducted in which both spoon and isokinetic sampling techniques were used to collect samples from the reaction shaft. The samples were then characterised by chemical, XRD and mineralogical analysis. Further information was acquired by measuring the oxygen potential and temperature at the bottom of the shaft using disposable probes. Comparison of the results of the two sampling methods showed that the spoon samples were devoid of material less than 25 m. Sulfur analyses on the samples provided information on the extent of reaction, plume shape and recirculation patterns. Disposable probe measurements showed the measurable particle temperatures ranged from 1150 to 1700 °C and that the material falling into the bath had a normalised oxygen potential similar to the slag. These latter measurements combined with the sulphur elimination and mineralogical analyses provided further information on the extent of reaction and enabled the reaction sequence to be ascertained.

Jan 1, 1999

By Amy Nelson

In the electrolytic production of zinc, cobalt is removed from the zinc electrolyte by cementation with zinc dust prior to electrowinning. Although the thermodynamics for this reaction are favourable, kinetic barriers to cobalt reduction render the method almost useless in practice unless activators such as copper and antimony or arsenic are added. There is a large body of work studying the effect of these additives, yet the mechanism by which they act is still poorly understood. Even when the target conditions are met, zinc dust consumption is excessively high: satisfactory operation requires up to 300 times the stoichiometric amount of zinc dust. The objective of this work is three-fold: (1) to examine the effects of activators and elucidate the characteristics that make a good activator; (2) to identify new additives that could lead to a more efficient purification process; and (3) to test the new additives with synthetic and real electrolyte solutions. The present paper gives a status report on this project.

Jan 1, 1998

By Yoshiyuki Matsui

As one of the factors of frequent troubles on iron-making blast in recent years, increased size of the blast furnace and high-productivity operation are pointed out. Consequently, great importance is attached to deadman shape and solid flow at the lower part of furnace. In the present study, firstly, the blast furnace raceway formation under the intensive coal injection by measurement of micro wave reflection gunned through a tuyere is discussed. As the flow rate of coke as the momentum of coke into raceway decreases by combustion of coal injected into tuyeres, the depth of raceway defined as the maximum position of micro wave reflection is easy to contract. It is expected that this new technology could detect the raceway collapse phenomena in short time and that the stability of raceway in coal injection is different from that in all coke operation. Secondly, the reduced stockline surface profile was measured by the reflection intensity of microwave struck from the furnace top after blow-off with stockline reduced, and investigation was made on the countermeasures for changes in the raceway depth and furnace body profile during operation. As a result, it has been clarified that flow-down of coke into the lower part of blast furnace and inflow into the raceway are greatly subject to the existence of deadman which is the packed structure of the lower part of furnace, and further, they are closely related to dynamic behavior of the raceway, and affect changes of the furnace body profile.

Jan 1, 2006

By Henry Hu, Alfred Yu

"A numerical model has been developed to simulate heat and mass transfer phenomena occurring during a novel magnesium reduction process-the vertical retort technology. The model was based on the control - volume finite difference approach. Simulations were run to determine the effect of various processing parameters on magnesium reduction cycle time. The model predicted temperature distributions, heating curves, recovery ratio of magnesium, and total process times. The predictions were used to optimize the magnesium reduction process including dimensions of the retort, geometries of the reactant compounds, and productivities. The results indicate that the implementation of the optimized processing parameters significantly decreases the reduction time, and consequently increases the production rate as well as lowers the energy consumption.IntroductionMagnesium consumption has been growing considerably in the past decade [1]. Of the total magnesium production, 30% is produced by the thermal reduction (Pidgeon) process, and it is anticipated to be still the main technology for producing magnesium in future [2]. One of the advantages of the Pidgeon process is that it is capable of producing high purity magnesium demanded by both the automotive and aerospace industries. However, the inefficiency of heat and mass transfer taking place in the horizontal Pidgeon reduction process results in low productivity, high energy consumption, labor-intensive operation, large floor space and high capital investment. This limits the production scale of a horizontal Pidgeon reduction process [3].Vertical reduction processTo overcome the shortcomings of the horizontal magnesium reduction process, a novel vertical magnesium reduction process [3] for large-scale production has been developed, in which heat and mass transfer in the retort is enhanced. The new process shortens reduction time, reduces energy consumption and increases productivity. The vertical reduction system is comprised of a vertically-placed retort, a heating furnace and a vacuum system. A section of the vertical retort is illustrated in Figure 1. Since the retort is set vertically, instead of horizontally, the entire procedure of loading the reactants material in the new process is different from the one for the horizontal reduction process."

Jan 1, 2001

By Akira Yazawa

To realize highly efficient process in extractive metallurgy, continuous operation nearly in equilibrium is preferable, but most metallurgical processes consist of plural steps with different chemical potentials. Traditional two-step process of sintering followed by reduction is continuous in each step, but is heterogeneous reaction system far from equilibrium, and the chemical potentials are varied considerably along the distance the charge travels in a reactor. This route will become old-fasioned in next century due to the various inherent problems caused especially by sintering process. To establish reasonable new smelting processes, the important tasks of the metallurgists are how to introduce feed and reacting gas in the reactor, and also how to overcome the difference in chemical potential in the reactor system. Based on the ways to solve theses tasks, recent proposals of new smelting process for copper and lead are classified and discussed with the help of sulfur-oxygen potential diagram. On such potential diagram, each equilibrium step in continuous smelting is expressed at a fixed point, and two reactors with different chemical potentials must be connected by continuous molten flow through launder or partition wall. In the latter case, the reactor is apparently single, but some technical problems must be overcome. While, in a batch smelting like converter, potential variation is successively realized along a path on chemical potential diagram with the time elapsed. To establish immediate equilibrium, continuous steady flow of reactants into well mixed reactor is indispensable. In modern smelting process, the ore is mostly supplied in the form of powder which have huge surface area and fluid character, and consequently injection process must be very attractive. Several examples are discussed for both of copper and lead smelting, and promising future technologies are suggested.

Jan 1, 1988

By D. C. Foguel, J. L. R. Bravo

For several years, Caraiba Metais S.A. (CMSA) had to stock the arsenic sludge generated from the electrolyte purification process of its tankhouse. The amount stocked · reached approximately 3,500 tonnes, as the effects of its recycling during the smelting process and consequently in the sulfuric acid plant were unknown. Besides, it had as limiting factors the high content of arsenic in the copper concentrates supplied by foreign countries as well as the reduced capacity of the tankhouse's purification plant. The choice for selling the mentioned residue, which generally contains more than 50% of Cu, was attractive, but the environmental policies and regulations had not allowed this option. Other alternatives, such as the production of bicupric arsenic by means of a solvent extraction process or arsenic trioxide, were considered but the economic feasibility was not attractive due to the absence of a domestic market and a poor international market. After a study of the arsenic partition in the metallurgical process, it was verified that the residue could be recycled without causing any operational problems or damage to the environment. To make this possible, the capacity of the purification plant was increased and the way of removing the arsenic sludge from the cells was modified from manual to mechanical, therefore avoiding the direct contact of the workers with this poisonous substance. Moreover, procedures for recycling in the smelter were established and tolerance limits were set for both the smelter and the sulfuric acid plant. The main amount of arsenic to be recycled is released with the smelting furnace off-gas, which is washed during the purification stage of the sulfuric acid plant. The acid water, rich in arsenic, is then treated in the waste plant and the arsenic, in its stabilized condition, is confined in an appropriate area.

Jan 1, 2000

By John K. Wright

The segregation process involves heating oxide-type ores with a halide salt in the presence of a solid reductant. By a complex series of cyclic vapour-phase reactions, the desired metal is extracted from its original position in the ore and segregated to the vicinity of the reductant. In this form it is then amenable to concentration by physical methods. In this work the segregation behaviour or eight different nickel laterite ores has been examined using a laboratory rotary kiln. It was found that the silicate (serpentine) ores responded better to the segregation conditions used than did the limonitic ores. An examination of the segregated metal particles showed that they consisted of ferro-nickel. The concentration of nickel in the metallics was sensitive to the ore types and the segregation roasting conditions.

Jan 1, 1994

By Florian Kongoli

Minor components and flux additions can modify the liquidus temperatures of multicomponent slags. In industrial practice, slags with various levels of minor components require various flux additions in order to achieve the lowest possible liquidus temperature The prediction and the optimization of these combinations can decrease the cost of the overall process. In this work the effect of several minor components and flux additions such as Al2O3, MgO, and CaO, on the liquidus temperatures of multicomponent iron-silicate slags has been analyzed in terms of a thermodynamic model Various simple isothermal and non-isothermal diagrams are presented. These diagrams can be used directly by the process operators to define the optimum conditions under which the fluxes can be used to achieve the desired slag liquidus temperatures.

Jan 1, 1999

By S. J. Kohut

Until recently SX-EW technology has only been used to produce conventional cathode for the cyclical commodity marketplace. Unlike electrorefining, SX-EW lends itself to the integration with the downstream manufacturing technologies for direct mine site production of value added products. The integration of SX-EW and downstream manufacturing results in the elimination of redundant process steps, the cost savings, and the access to value added product markets which can buffer the producer from swings in the cathode market. SX-EW production of copper powder and powder-based products has been demonstrated at the pilot plant level. The SX-EW process has been successfully redesigned to meet the more specific demands of engineered products. Challenges include the solution purity, the cell ventilation, the high current density operation and the product handling. Successful demonstration of mine site production of value added SX- EW products opens up new non-commodity marketplaces to the mining industry.

Jan 1, 1999

By B. C. Curson

A comprehensive simulation of .the gas handling system in BHP Copper's San Manuel smelter was developed using AFT Fathom software, with the objective of minimizing SO2 emissions while maximizing smelter throughput. Once verified with plant data, the simulation quickly revealed' the complex interactions occurring between individual converters and the flash furnace. The increased understanding provided by the simulation allowed novel, counter-intuitive control strategies to be developed and tested successfully.

Jan 1, 1999

By R. Gampala

The consolidation of mom matrix composite monotapes occurs by the plastic (time independant) and creep deformation of monotape asperities. Past models of the process used seperate micromechanical analyses of the contact deformation by (rate independent) plasticity and power law creep (i.e steady state creep). These models are now used to simulate consolidation and to optimize/control consolidation process cycles so that the composite's microstructure is "steered" to, a user defined goal state. However, the models do not incorporate the sometimes dominant transient creep process and the instantaneous response of the plasticity mechanism causes finite discontinuities in the microstructure state vector field and therefore eliminates the possibility of using the powerful array of trajectory optimization schemes that all require continuous vector field for optimization and control. To overcome this problem, a inified creep/plasticity constitutive model that results in a continuous state vector field is used to rederive the contact deformation response during monotape consolidation. The contact blunting of a laterally constrained hemispherical asperity is first analyzed and its response represented by two coefficients; one relating the contact area to the blunting strain (C), the second, the mean contact pressure to the blunting rate (F).The C and F coefficients for this unified blunting problem are then obtained by finite element analysis, and detailed results presented for two composite matri-ces of topical interest (Ti-24A1-11Nb and Ti-6Al-4V).

Jan 1, 1996

The entrainment of copper matte in the slag during the slag skimming stage of a Peirce-Smith converter was studied with a dam break model. Experiments were carried out with a range of fluid pairs where the lighter fluid was allowed to overflow a weir and the amount of entrained heavier fluid measured. The resulting entrainment is measured as the ratio of the heavy to light fluid withdrawn. The fluids include oil-water, water- glycerol and salt solutions-water pairs to cover a wide range of densities and viscosities. It was found that the Richardson number, Ri, correlates the entrainment well. For the case of the liquid-liquid interface initially at the same height as the weir, the entrainment was found to vary with Ri-1/3. The transient flow was simulated with a volume of fluid (VOF) code written in-house and used a stairstep approach to represent flow obstacles. The code was validated against the experimental results with good agreement for the variation of the heights of the two fluid with time. The simulation showed that the prevailing mechanism for entrainment is due to a pressure differential created across the liquid in the converter during pouring resulting in the heavier liquid being rotated upwards and over the weir.

Jan 1, 1999

By C. T. Yavuz

Higher environmental standards have made the removal of arsenic from water an important problem for environmental engineering. Iron oxide is a particularly interesting sorbent to consider for this application. Its magnetic properties allow relatively routine dispersal and recovery of the adsorbent into and from groundwater or industrial processing facilities; in addition, iron oxide has strong and specific interactions with both As(III) and As(V). Finally, this material can be produced with nanoscale dimensions which enhance both its capacity and removal. The objective of this study was to evaluate the potential arsenic adsorption by nanoscale iron oxides, specifically magnetite (Fe3O4) nanoparticles. We focused on the effect of magnetite particle size on the adsorption and desorption behavior of As(III) and As(V). The results show that the nanoparticle size has a dramatic effect on the adsorption and desorption of arsenic. As particle size is decreased from 300 nm to 12 nm the adsorption capacities for both As(III) and As(V) increase nearly 1000 times. Interestingly, this increase is more than expected from simple considerations of surface area and suggest that nanoscale iron oxide materials sorb arsenic through different means than bulk systems. The desorption process however, exhibits some hysteresis with the effect becoming more pronounced with small nanoparticles. This hysteresis most likely results from a higher arsenic affinity for magnetite nanoparticles. This work suggests that magnetite nanocrystals and magnetic separations offer a promising method for arsenic removal.

Jan 1, 2006

By Levent Özmen

Colemanite is a mineral containing varying amount of boron that is found in abundance in Turkey. It has a good possibility to be used as a flux in iron and steel industry. In this study a review of the use of colemanite, as a flux agent in steel production has been carried out and various related aspects such as its influence in metal-slag reactions, solubility of lime and magnesia in the slag are discussed along its performance in several points of views including its technical and environmental usage characteristics. Positive and negative factors of using this material as a flux are also underlined.

Jan 1, 2006

By A. Kapilashrami

Slag foaming proves to be both blessing and curse for the process productivity, depending on where in the process it occurs. In pyrometallurgical processes, slag foaming is often a result of chemical reactions taking place in the slag. As the slag composition and reaction rates are changing, foaming occurs under dynamic conditions. In the present work, slag foaming was studied with XRF. The foam displayed a fluctuating behaviour, unaccountable by existing models. The concept of foaming index was found not to be satisfactory in describing the foam, resulting in the need for alternative theories. The rate of fluctuations was seen to be related to the difference between rate of gas generation and rate of gas escape from the system (Ug-Ue) as well as the bubble sizes. Thus, model development of dynamic foaming phenomenon has to take the effective chemical reaction rate as well as the bubble sizes into consideration. The first step in obtaining foam is to form bubbles. In the present work, gas bubbles were generated through chemical reaction at interface between two immiscible liquids and the bubble formation was studied optically. The gas bubble size was seen to be uninfluenced by the reaction rate. However, bubble formation was seen to take place in one of the phases and since the bubbles consequently traversed the interface under the influence of buoyancy, the viscosity of the first phase was found to influence the final bubble size where increased viscosity would yield a larger bubble size.

Jan 1, 2006