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By Ayşe Ece Yıldızçelik, Mehmet Buğdaycı, Onuralp Yücel

ZrB2 and TiB2 are significant metal borides. They are being used in various industrial areas from space technology to nuclear industry owing to their physical properties such as high melting point, high thermal/electrical conductivity and low density. Present study was conducted in two main stages: self-propagating high-temperature synthesis (SHS) reactions and leaching. ZrO2, TiO2, B2O3 were used as starting material and Mg was used as a reductant to produce ZrB2-TiB2 powders via SHS. Therefore, it was aimed to determine production parameters, leaching conditions and comprehensive examination of final product features. The samples were characterized by using chemical analysis (AAS), XRD, XRF and SEM/EDS techniques.

Jan 1, 2015

By Kazue Moriya

At the 1980 TMS-AIME world symposium, Dr. Davey mentioned that the traditional lead blast furnace is now being challenged by direct smelting processes. In the copper smelting field both the blast furnace and reverberatory furnace are also disappearing in favour of direct smelting processes such as Outokumpu flash smelting, Mitsubishi continuous smelting, Noranda furnace, Inco furnace and so on. Those new processes all have the following in common: (1) High degree of mechanization (2) Metallurgical reactions carried out in closed vessels (3) Application of oxygen and/or oxygen enriched air (4) Minimization of handling materials and gaseous volume (5) Minimum energy requirements (6) Removal of workers from near the furnace (7) Reduction of emissions of harmful gas to meet environmental regulations. (8) Improvement to the work place environment to avoid occupational hygiene hazards. Direct and continuous smelting of powdered concentrate in one vessel was a romance of the metallurgist since early times. However as mentioned above, in the copper field this objective is being achieved in practice. The industry however can't deny that the serious and severe regulation of environmental pollution in every country was the prime motive for the modernization of smelters. In early days, to meet regulations, it was anticipated that many economic difficulties such as higher capital and energy costs and extravagant use of resources and waste disposal would be the result. "Turn a misfortune into a blessing" is an old saying which reveals the current thinking and reacent developments in the nonferrous industries. In the last ten years in the lead smelting field, about two decades later than copper, commercial scale smelting using new furnance technology has started. The KIVCET process and QSL process, which is flash smelting and bath smelting respectively, are becoming major competitors. They will be sure to upgrade their processes to remain economically and environmentally viable in the comming decade.

Jan 1, 1990

By G. G. Krishna Murthy

Interactions of wustite and hematite pellets with Fe-C melts were investigated experimentally by examining the effect of pellet size and bath temperature on the reduction rates of the pellets. Experiments were carried out in the temperature range 1473-1923 K. A flash X-ray equipment was used to obtain images of the melt surface during its reaction with an oxide pellet. The reduction rates were calculated using experimentally estimated time for complete reaction of a pellet, tR. The value of tR was determined employing gas mass flow rate, or pressure rise in the sealed furnace, versus time traces. The value of tR was the same for both wustite and hematite pellets of equal weight at or above 1723 K and it decreased with increasing melt temperature. But the reduction rate was substantially lower at temperatures below 1651 K, the melting point of wustite. The rates were defined as the rate of moles of oxygen removed from the pellet per unit area of bath free surface and it was found that the bath surface area affects the reduction rates. It was established that the overall reaction followed nth-order rate kinetics with the values of n falling between 0.3 and 0.4 for temperatures above the melting point of wustite. The apparent activation energy determined using the apparent rate constants obtained from the experimental data was 76.2 + 27.7 kJ/mol-O.

Jan 1, 1992

By André L. B. Bittencourt

The copper content in the waste slag represents the greatest loss in the process of Caraíba Metais' Smelter. By identifying the variables responsible for copper stabilization in the slag, a minimization on these losses is expected, producing a granulated waste slag with a copper content lower than 0.7%. Statistics resourses such as control charts, Pareto's diagram and correlations curves were applied for the data obtained in the first semester of 1992. The magnetite and the calcium oxide contents in the slag of the Flash Smelter Furnace were most prominent variables. Some operational changes introduced during and after this investigation have shown good results.

Jan 1, 1994

By Jean P. Murray

The extractive metallurgical industry is a major consumer of high-temperature process heat. It is, consequently, a major contributor of C02 emissions and other greenhouse gases derived from the combustion of fossil fuels for heat and electricity generation, or from the process itself. These emissions can be substantially reduced by replacing fossil fuels with solar energy as the source of process heat. Concentrated solar radiation can supply a large amount of thermal energy to endothermic reactions at temperatures exceeding 2000 K. Another potential for C02 emission reduction exists as well. Thermodynamically, the total amount of energy required for metal production at any given temperature is the enthalpy change of the reaction, AH. Of this total, an amount equal to the Gibbs free energy AG must be supplied as high quality energy in the form of electrical work or by using a reducing agent. Many conventional metallurgical electrolytic processes and reducing furnaces are unable to add only the thermodynamically required electricaVchemical energy due to process inefficiencies. Electrical work in excess of AG for the reaction may be used to supply process heat, or excess chemical reducing agent burned to supply process heat. Besides the thermodynamic and economic drawback, this inefficiency results in excess C02 emissions derived from the combustion of fossil fuels. With these practices, energy becomes an important cost element of the metal produced. Highly-concentrated solar energy has the demonstrated potential to separate these two forms of process energies, allowing the addition of only the thermodynamically required high-quality energy while high-temperature solar process heat is provided to the reactor. Examples of metal oxide reduction processes that have been studied experimentally in solar furnaces include the production of Fe, Al, AI/Si alloy, Mg, Zn, Tic, Sic, CaC2, TIN, Si3N4, and AIN by carbothermic reduction of their oxides, and the high-temperature solar- electrothermal reduction of ZnO.

Jan 1, 1999

By Denis Shishin

The pyrometallurgical production and recycling of non-ferrous metals involves the use of complex feed stocks, having awide range of chemical compositions from sources that include mineral sulphide concentrates, high value obsolete materials and process wastes. The commercial viabilities of these operations hinge on the ability to extract value from these materials. Increasingly, modern computer-based tools are used to describe and predict process outcomes, including mass and heat balances, the partitioning of elements and phase equilibria. At the heart of these predictive tools are thermodynamic databases that describe the fundamental chemical properties of a system and all the components present. A comprehensive research program has been established to develop an accurate, self-consistent thermodynamic database describing all gas-slag-matte-metal-speiss-solid phases in the system Cu2O-PbO-ZnO-Al2O3- CaO-MgO-FeO-Fe2O3-SiO2-S-(As-Bi-Sb-Sn-Ag-Au). The database can be used in conjunction with the FactSage computer platform. The accuracy of the database and its application to industrial practice is demonstrated.

By Lanre Oshinowo

Computational Fluid Dynamics (CFD) is used in conjunction with process modelling at HATCH to achieve a superior level of confidence in the process design of hydrometallurgical process plants. The use of these tools to evaluate designs through virtual prototyping reduces the risks associated with making design decisions. This paper highlights the development of a co-simulation strategy at Hatch for the seamless integration of process modeling software addressing different scales (process time and space): flowsheet level models and .equipment level models. With co-simulation, the process design engineers can improve design accuracy, troubleshoot and optimize performance and influence decisions impacting equipment operation by representing specific unit operations in the flowsheet model software with detailed CFD models. Specifically, this paper will focus on the co-simulation of a Ni/Co high-pressure acid leach (HPAL) process including heaters/heat exchangers and flash system, autoclave and quench/scrubber system. The knowledge developed can be transferable to other processes.

Jan 1, 2004

By D. J. Chaiko

Aqueous biphasic extraction (ABE) processes offer the potential for low-cost, highly selective separations. This countercurrent extraction technique involves selective partitioning of either dissolved solutes or ultrafine particulates between two immiscible aqueous phases. The extraction systems that we have studied are generated by combining an aqueous salt solution with an aqueous polymer solution. We have examined a wide range of applications for ABE, including the treatment of solid and liquid nuclear wastes, decontamination of soils, and processing of mineral ores. We have also conducted fundamental studies of solution microstructure using small angle neutron scattering (SANS): In this chapter we review the physicochemical fundamentals of aqueous biphase formation and discuss the development and scaleup of ABE processes for environmental remediation.

Jan 1, 1996

By H. K. Fouad, L. A. Guirguis

The starting mill strip solution· for this study· is an ammonium uranyl tricarbonate solution of pH 8.2 containing 20g uranium/liter, after a DEPA/TOPO extraction process from sulfuric acid leaching liquor. To the first portion of the concentrated acidified strip solution, hydrofuoric acid is added at 95°C in reduced condition to obtain uranium tetrafluoride. The second portion of the uranyl carbonate strip is subjected to a precipitation step by admixing 0.3 volume of non-solvent precipitating agent such as acetone per volume of uranium. ·Uranium oxide (U30 8) is obtained from this precipitate by calcination for half an hour at 800°C in air. The third portion of the strip solution is neutralized to a pH 6.5 with sulfuric acid to precipitate iron and other contaminants. The solution is further acidified to a pH 1.85 with continuous air bubbling to remove CO2, followed by H2Ch precipitation at pH 3.5 to obtain uranyl peroxide. The latter is reduced by stannous chloride to obtain uranium trioxide dihydrate UO3. 2H20. Identifications, characterization· and purity of these products are carried out by complete chemical analyses, Scanning electron microscope study, tap density determination, X-ray diffraction and infrared spectroscopic investigations. The achieved results agreed well with that of the published data for these nuclear grade purity products.

Jan 1, 2000

By R. H. Crist

Reactive components of algal cell walls include uronic and alginic acids: In addition, many marine species have half ester sulfate groups which function as fixed anions. Associated metals vary with the media, eg., Ca and Mg in fresh water (FV) and Na, Ca, Mg in seawater. . These metals readily exchange with aqueous phase protons or metal cations. A plot of the total amount of metal cations displaced by protons vs .. pH shows one inflection at pH 4 for FV algae and' in addition a second inflection at pH 2, 3 for marine algae. The first inflection is interpreted as. Indicating the cations associated with carboxyl groups ,and the ,second with half ester ?Sulfate groups. The exchange capacities of various aigal ,species vary widely. When FV algae is placed in a Pb2+ solution,- the amount of Pb2"' deposited on the algae is. Equivalent to the. Total Ca2?, Mg2, and H+ displaced? thereby confirming the ion exchange mechanism. Ion exchange equilibrium constants are reported for the displacement of ca2+ from Vaucheria. With Mg2+, sr2+, Cd2+, Pb2+_ and Na+ as well as the reverse reactions. Cd2+ can .be removed partially from algae by precipitating it as CdS or Cd(OH) 2 Pb2+ and Cu2+ are also partially removed as the hydroxides. Rates of reaction for various alkali hydroxides decrease with increasing .unhydrated cation radius. It is concluded that theory is useful in predicting viable applications for algae in pollution abatement.

Jan 1, 1991

By S. A. Davis

In July of 1996, the Kroll process began production again at TIMET's Henderson, NV, manufacturing facility. This, after being shut down for several years due to low market demand for titanium. Faced with limited pond capacity and increasing costs for water and wastewater disposal and storage; process changes were made to recycle water used to wash Kroll titanium sponge back into the sponge leaching process. This idea was revisited from 1992-93, when three consecutive attempts to recycle water for this application were unsuccessful due to early pump failure. Since it was uncertain why previous attempts failed, a complete understanding of the existing system was first sought. This included reviewing piping and flow diagrams; taking field measurements for all the piping, valves, and fittings; analyzing the wastewater composition; and modeling the fluid dynamics and control of the system. The fluid dynamics of the system were modeled by breaking the piping network up into nodes and applying the Bernoulli equation to each segment. The fluid flowrate control valves were modeled for this purpose also and the models were used to help specify the required processing equipment and control ranges and tolerances. Once the project was completed, an operating procedure was prepared for operation, startup, and shutdown of the washer water recycle system.

Jan 1, 1999

By I-Min Lu

An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces. The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.

Jan 1, 1996

By Varadarajan Seshadri

A physical model based on similarity principles was constructed for simulating the RH degasser of CST (Companhia Siderurgica Tubarao, Vitoria, ES, Brazil) to evaluate the circulation rate of the metal which essentially defines the degree of exposure of the metal to vacuum in the chamber and thus of the refining rate, The circulation rate on the other hand will influence the decarburization rate and removal of dissolved gases like nitrogen and hence it is essential to optimise this parameter to get maximum refining efficiency with minimum refining times, thus improving the productivity of the secondary refining process. Mixing characteristics in the ladle is evaluated by pulse tracer addition using conductivity-meters located at the down leg as well as at several locations in the ladle. The influence of gas injection through nozzles in the upleg with simultaneous bottom injection of gas as well as nozzle blockage on the circulation rates were investigated. Also simulation experiments of kinetics of decarburization were carried out using CO2 adsorption-desorption process in sodium hydroxide solution as circulating fluid and the effect of, bottom gas flow rate in this case was also evaluated. The results were carried over to prototype and to optimize the process.

Jan 1, 2003

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By S. Abe

An extensive study has been carried out to determine the true cause of floating slimes precipitation which sometimes occurs and badly affects the quality of copper cathodes. Soluhilities of floating slime compounds systematically measured for the ternary system As-Sb-Ri added solely or in combination with conventional copper electrolyte (63°C) and bench scale electrorefining experiments done by varying electrolyte composition, have shown conclusively that the level of Sb(V) ions plays a substantial role in the precipitation mechanism. It was, therefore, speculated that controlling the level of the less soluble S b ( V ) ions below a certain critical level should result in a complete elimination of the undesirable precipitation. This can be easily achieved, for instance, by the addition of a reducing agent such as SO2 gas and the simultaneous employment of a certain type of cheating agent that effectively removes excessive Sb and Bi from the contaminated electrolyte. Long-term pilot testing conducted in line with the above speculation has confirmed the SO2/chelating resin scheme to be industrially very attractive and feasible.

Jan 1, 1987

By P. A. Treasure

The EMEW® cell has been developed to overcome a number of inherent limitations in conventional electrowinning technology, particularly the high cost and restricted process windows characteristic of conventional hardware. The technology has been widely demonstrated to achieve high performance for various metals under chemical conditions well outside the limits required for efficient operation of conventional cells. This process flexibility offers significant opportunities for cost savings. in recovery of zinc from primary and secondary sources. The EMEW® technology is now available on a fully engineered basis, as a versatile commercial alternative to conventional electrowinning hardware. Application of the EMEW® cell for recovery of secondary zinc material offers significant advantages to the recycling industry. For example, a selective caustic leach can be used where there are high levels of iron or other contaminants in the target material. The reagent requirement is minimal as most of the caustic is regenerated in the bell and zinc dust that may be required for electrolyte purification is produced in the cell. A high purity zinc powder or cathode is produced in the cell. In the case of acidic zinc electrolytes, the cell is capable of operating over a much wider range of operating conditions than a conventional cell.

Jan 1, 2000

By J. D. Miller

Low-level radioactive contaminated soils (10-500 pci/gm) created by defense-related activities at certain superfund sites, such as Nevada Test Site (NTS), is a current environmental concern. Many of these contaminated sites may require appropriate cleanup and restoration, which could cost billions of dollars and put tremendous pressure on our limited financial resources. Therefore, the development of a selective flotation process to separate such radionuclides from contaminated soils should be considered. In this study, both a pure depleted UO2 sample and three synthetic UO2/soil mixtures were used to evaluate surface chemistry features and to examine the possibility for the flotation of fine UO2 particles from selected soils. It was intended that this model system would be a reasonable representation of contaminated soils such as those found at the Nevada Test Site which are reported to be contaminated by PuO2 fallout. The effect of reagent schedule, particle size distribution, and surface charge are discussed with respect to the flotation separation of the UO2/soil mixtures. It was found that both commercial fatty acids and reagent grade sodium oleate are effective collectors for UO2 flotation provided the pH is adjusted to the range of pH 8-9. The bench-scale flotation results successfully demonstrated that froth flotation technology can be used to remove UO2 from such model contaminated soils with appropriate flotation chemistry conditions which depend on the soil characteristics and other pretreatment procedures. In the best case, 90.2% of the UO2 was removed from a UO2/NTS soil mixture (119 ppm UO2) and the soil reduced in UO2 contamination from 119 ppm to 17 ppm in a single stage bench flotation. The impact of clay slimes present in the soil is revealed by the results which show that, for example, for a deslimed soil (28x400 mesh and 100 mg UO2/kg soil) 85¬90% UO2 recovery can be obtained with a reduction in contamination to 4.6 mg U02/kg soil.

Jan 1, 1995

"The theoretical basis of ideal smelting reduction using coal as reductant in a process employing closed loop forced-circulation of hot metal is outlined. In the proposed process, an extensive area of relatively slag-free hot metal is available as a heat sink for absorbing the large amount of heat produced by complete combustion of CO within the furnace. Any slag that is formed within the oxidizing arm of the furnace loop is quickly swept away as a thin floating layer by the bulk movement of hot metal which is induced positively by forced melt circulation and sustained by causing the hot metal and the thin slag layer to overflow into a lower level hearth in which coal is carbonised and dissolved directly into the circulating melt.The proposed process is shown to offer very substantial cost savings over all other direct smelting technology. This is mainly because of its inherently low capital cost and its high energy efficiency. Furthermore, the favourable economics are not reliant on fuel gas credits as all the process gas is combusted within the reactor itself.IntroductionMetallurgical processes in the year 2000 will be compromise solutions to the metallurgical problems that already exist today. It is common knowledge that the mineralogical complexity of certain polymetallic sulphides, for example, precludes high degrees of separation and recovery by conventional mineral beneficiation. steps are therefore being taken towards the development of a truly polymetallic smelting process which will produce simultaneously zinc lead and copper as, metals from complex ores without prior beneficiation(l). In the ferrous extraction industry, the shortcomings of the highly efficient modern blast' furnace are well known and world-wide there is considerable effort being directed towards coal-based ironmaking without the requirement of metallurgical coke as a process intermediate. The current status 0f2Joal-based ironmaking has recently been reviewed by Smith and Corbett. (2)"

Jan 1, 1988

By Emmanuel N. Zevgolis

After the Krupp-Renn process was shown to be unsuitable for treatment of the Greek nickeliferous laterites, the LM process was developed. It involved roasting reduction up to metallic iron in a Rotary Kiln (R/K) and smelting in an Electric Furnace (E/F). Ferronickel (with 15% Ni) produced in the E/F, was upgraded to 90-95% Ni in an 02 converter. Raw Ni was then electrolyzed to pure Ni. The LM process was not applied for very long however, due to various problems. So, the Larco process was developed, i.e., pre-reduction in R/Ks, smelting of the calcine in E/Fs for ferronickel production (15% Ni) and enrichment to 20% Ni, in an O2 converter. Until now, many technological improvements have been invented and applied or adjusted to the process, which have made it a fully reliable and competitive one. sohe of the improvements were the invention and application of a new granulation process for liquid ferronickel, the modification of the existing R/Ks, E/Fs and converters and the design of new ones, and others that are described in the paper. Keywords: Ferronickel, metallurgy, laterites, LM process, Larco process

Jan 1, 2004

By A. Galvan

High rate compressible media filter (CMF) tests produced exceptional total suspended solids (TSS) removal at hydraulic loading rates ranging from 97.8 to 122.2 m/h. The compressible media is manufactured from a robust resin fiber that can withstand low pH and temperatures up to 149 °C. The media porosity can be varied by applying compression onto the media. At 40% compression, the CMF can remove particles greater than 4 μ. Three synthetic test-samples were generated by Hazen Research Inc., (Golden, Colorado) to simulate the copper Pregnant Leach Solution (PLS), Raffinate and Electrolyte solutions used for the testwork conducted at their facility. The preliminary results showed that the CMF was very effective in removing TSS without the use of chemical conditioning from the above test-solutions with efficiencies of 98%, 97%, and 96%, respectively. Given the remarkably high hydraulic loading rates, the industrial equipment footprint would be minimized appreciably over conventional clarification and alternative filtration systems.