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By Gus Van Weert

Solvent extraction of iron from zinc refinery liquors has been investigated before, mainly on the MEHPA / HC1 stripping combination. Leakage of chloride into the zinc electrolyte and the costs of handling the ferric chloride eluate have prevented this option from being adopted. This work explores the stripping of the ferric loaded organic phase with nitric acid to take advantage of the possibility of regenerating up to 6N nitric acid, and clean spheroidal hematite production by autoclave treatment of ferric nitrate solution. The work was carried out with DEHPA (di 2-ethyl-hexyl phosphoric acid) in kerosine. Degradation testing proved the DEHPA to be very stable, when exposed to nitric acid solutions up to 6N and temperatures up to 70" C over a period of five days. Ferric iron was removed completely froma synthetic hot acid leach liquor, irrespective of the DEHPA concentration. Stripping the ferric turned out to be the problematic step. Although the stripping efficiency was considerable better at 50 than at 20° C, it decreased with increasing DEHPA/Fe ration in the organic phase. Eluates of no more than 5-10 g/l ferric nitrate were produced. surprisingly, nitric acid was found to be a less efficient stripping agent than sulphuric at equivalent normality and its efficacy levelled off above 4N. It was concluded that DEHPA does not appear to be the S.X. reagent to take advantage of the low cost autoclave decomposition of ferric nitrate opportunity in zinc hydrometallurgy and that another S.X. reagent, also resistant to nitric acid, but based on weaker compound formation is needed.

Jan 1, 1998

By J. Gartelmann, B. Zaslavsky, Y. Vojta, D. J. Chaiko, W. Mego, A. N. Rollins

"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.IntroductionAqueous biphasic extraction (ABE) is a highly adaptable separation technique that can be used in a wide range of applications. We have been evaluating various types of ABE systems for possible applications in the treatment of solid radioactive wastes (1,2), liquid nuclear wastes (3,4), and contaminated soils (5-7), and in the removal of organics from aqueous salt solutions (8). We have also conducted fundamental studies of the solution microstructure of ABE systems using small angle neutron scattering (SANS) (9).The extraction systems are generated by combining an aqueous salt solution and an aqueous polymer solution. This produces two distinct liquid layers that are as immiscible as oil and water, yet each liquid layer contains at least 70 to 80 wt % water. The biphasic systems that we have been working with consist of immiscible polyethylene glycol (PEG) and salt solutions. Some inorganic salts that promote biphase formation with PEG solutions include the sodium/potassium salts of sulfate, carbonate, phosphate, and hydroxide (10)."

Jan 1, 1996

By Balladares V. Eduardo

Most of the arsenic contained in copper concentrates is removed in the gas phase during the smelting and converting processes and, according to recent environmental regulations, it is required to fix it in a solid stable form. In this regards, ferric arsenate has been reported as thermal and aqueous stable compound. Therefore, various alternatives for treating gas containing arsenic were considered in this work. From data obtained at laboratory scale on fixation of arsenic using iron oxide, a new process to treat copper concentrates containing arsenic was evaluated. The effect of temperature, oxygen potential and the sample porosity on the fixation of arsenic contained in a gaseous stream was studied, and the iron oxide converted into ferric arsenate was up to 10%. The obtained results suggest a new alternative for gas treatment with an interesting and attractive technical development. The arsenic was retained as ferric arsenate with thermal and aqueous stability, and it allows a safe disposal keeping the environmental restrictions. The kinetics parameters are used to scale up laboratory results to higher processing rates.

Jan 1, 2005

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By Walter E. Dean

Twenty six samples of carbonaceous gold ores and associated rocks from outcrop and mine localities in northcentral Nevada were analyzed for concentrations of major. minor, and trace elements, total sulfur, and organic carbon. Q-mode factor analysis was used to define six distinctive carbonate, organic, and detrital associations of elements, and to group samples based on these associations. The trace metals that have clearly enriched the organic-carbon-rich samples are V, Zn, Ni, Cu, Cr, and Mo, although few of the samples could be considered "metal-rich" when compared to other organic-carbon-rich black shales. Rock-Eval pyrolysis was used to evaluate thermal maturity and hydrocarbon yield of the samples. Unfortunately, most samples were too thermally altered to be suitable for routine organic geochemical characterization of organic matter. The 813C values of organic carbon in rocks from different deposits have a trimodal distribution, but there is no clear distinction between the three groups of deposits that can be related to age, thermal history, or depositional environment.

Jan 1, 1987

By M. Pakala, Z. Fan, Ray Y. Lin

Deposition of hard chromium coatings using electrodeposition is accompanied by emission of hexavalent chromium mists which is a carcinogenic. Hence alternative chromium deposition technologies are being investigated. Sputter deposition is a strong candidate to economically deposit hard chromium coatings in an environmentally friendly way. Chromium coatings of 2-3 µ m thickness were deposited on plain carbon steel coupons using RF magnetron sputter deposition. Depositions were carried out with 0 to 22 vol% nitrogen in the plasma. Structure of the coatings was studied using x-ray diffraction analysis With increasing nitrogen contents, formation of the two nitride phases was observed. The pure chromium phase was detected in coatings with up to 7% nitrogen in the sputtering gas. The solid solution of nitrogen in the pure Cr phase coating was identified by shifts of Cr x-ray diffraction peaks to higher d-spacing. The microhardness of the coatings deposited at a substrate temperature of 200°C showed an increase in hardness with increasing nitrogen content from 600 kgf/mm2 (5.9 GPa) at 0% nitrogen to I250 kgf/mm2 (I2.25 GPa) at 9.5 % nitrogen and a subsequent decrease in hardness to I 100 kgf/mm2 (11 GPa) beyond 9.5 % nitrogen in the sputtering gas. This corresponds to the formation of the hard Cr2N phase, at 9.5 % nitrogen, and CrN phase, at I5.7 % nitrogen. The reported bulk hardness values of Cr2N and CrN are I600 kgf/mm2 (I5.7 GPa) and I 100 kgf/mm2 (11 GPa) respectively. For pure Cr phase coatings, there is a slight increase in hardness for coatings deposited at 7. I % nitrogen from that without nitrogen in the sputtering gas. This could possibly result from the solid solution strengthening of the Cr lattice by nitrogen. For films deposited at 200°C, phases of the deposited films seem to be the overwhelming factor in controlling the microhardness.

Jan 1, 1998

By Qingchun Yu, Baoqiang Xu, Yongnian Dai, Bin Yang, Fulong Zhu

"In this paper, the mechanism of the carbothermic reduction-chlorination process to extract aluminum from alumina in vacuum was investigated. The carbon monoxide (CO) content of the gas, phases of the reduction slag, surface morphology of the reduction slag and the product aluminum were measured by means of gas chromatography (GC), XRD, and SEM. The experimental results indicated that the content of CO in the gas decreased, but Al4C3 increased with time at 1773K during the carbothermic reduction process of alumina. AlCl(g) and graphite (C) were produced by the reaction between Al4C3 and AlCh(g) at 1773K, and then aluminum beads generated after the decomposition of AlCl(g). It implied the mechanism of alumina carbothermic reduction-chlorination process in vacuum involves three steps as follows: the carbothermic reduction of A}z03 to produce Al4C3, the chlorination of Al4C3 by AlCh(g) to produce AlCl(g), and the decomposition of AlCl(g) to produce Al(l).IntroductionAluminum is the basic raw material for many industries [1], and it is used extensively because of various excellent properties such as light weight, good malleability, high strength, excellent thermal conduction, high corrosion resistance and so on [2]. Industrial production of aluminum currently includes refining alumina and electrolytic aluminum processes. However, its development has been effected by some factors such as high energy consumption and heavy environmental burdens [3]. In the past several decades, there had been numerous attempts to produce aluminum by new methods. Extracting aluminum from alumina or bauxite directly by carbothermic reduction-chlorination process had been studied [ 4-6]. Although the alumina carbothermic reduction process [7~9] had been studied, the mechanism of the carbothermic reduction-chlorination process had not been systematically elucidated.In order to investigate the mechanism of the carbothermic reduction-chlorination process in vacuum, GC, XRD and SEM techniques will be used to determine the CO content and to characterize the surface morphology and composition of the slags at various temperatures."

Jan 1, 2011

By V. I. Lakshmanan

Wastes when produced can be reused or recycled prior to disposal. Industries that cause environmental concerns during manufacturing include primary materials and primary metals. Pollution prevention mechanisms to achieve waste reduction require new separation, reclamation, control and process simulation technologies. Substituting recyclables for virgin resources will reduce energy use, water pollution, air pollution, water use and mining wastes. Shrinking landfill space will spur new technologies for waste treatment and recycling. These situations hence offer opportunities for innovative flowsheets with appropriate separation technologies. Development of innovative flowsheets to treat recyclables offer unique opportunities for process/product development, obtain green products and hence market advantage. The paper will illustrate with selected innovative flowsheets to treat recyclables.

Jan 1, 1996

By Donald R. Sadoway

"Molten salt electrolysis is a proven technology for the extraction of metals -- all· the world's primary aluminum is produced in this manner. The unique properties of molten salts also make them excellent media in which to treat a variety of forms of waste. Of special note in this regard is electrolysis in molten oxides, a concept put forward by the author, initially as a ""clean technology"" for producing primary metal. However, in the context of waste treatment, electrolysis in molten oxides is a process offering the prospect of changing the-valence of dissolved heavy metals while making pure oxygen gas as the main by-product. Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3, SiO2; CaO, and MgO have confirmed electrochemical production of oxygen on a carbon-free anode. IntroductionMolten salt electrolysis is the electrolytic decomposition of a compound dissolved in an ionic melt. The prime example of this process can be found in the production of aluminum. The compound, alumina (Al2O3)' derived from the mineral bauxite, is dissolved in an ionic melt comprising a multicomponent solution of cryolite (Na3AlF6)' aluminum fluoride (AlF3)' and calcium fluoride (CaF2,). The products of electrolysis are molten aluminum and carbon dioxide, the latter due to the attendant consumption of the carbon anode. Primary aluminum is produced in a reactor known as the Hall cell.' Alternatively, the compound undergoing electrolytic decomposition can be derived from waste. Processing in molten salts, with their capacity to dissolve materials to very high concentrations compared to those attainable in aqueous solutions, can be rather advantageous. High solubilities lead to high limiting current densities, and this, in tum, results in high productivities: For a primer on molten salt electrolysis and a review of the basic literature in the field of molten salts the reader is directed to an earlier publication of the author (1)."

Jan 1, 1996

By Donald R. Sadoway

Molten salt electrolysis is a proven technology for the extraction of metals -- all the world's primary aluminum is produced in this manner. The unique properties of molten salts, also make them excellent media in which to treat a variety of forms of waste. Of special .note in this regard is electrolysis in molten oxides, a .concept put forward by. the author, initially as a ."clean technology" for producing primary metal. However, in the context of waste treatment, electroly-sis in molten oxides is a process offering the prospect of changing the. valence of dissolved heavy metals while making pure oxygen gas as the main by-product .Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3 and MgO have confirmed electrochemical production of oxygen on a carbon-free anode.

Jan 1, 1996

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FexAs2O2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS203 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Lamar S. Todd

The direct production of metal from a sphalerite concentrate is an attractive route for primary zinc. A series of operations and conditions have been selected to efficiently cause the following overall exothermic reaction. The process uses a continuous circulation of molten copper for material and energy transfer between the unit operations. Sulfide concentrate is reduced with an excess of superheated copper to make a copper alloy and white metal. The alloy is stripped of volatile metals under vacuum and some metals can be separately condensed. The residual copper and the white metal are fed into a copper converter to be blown with oxygen for desulfurizing and the superheated copper is recycled. The paper will include a detailed material flow sheet for the process, discussion of the operating conditions of the individual units, behavior of minor elements, and zinc quality.

Jan 1, 1999

By J. S. Pitsillos

A new furnace tapping technique involving the simulation of a control valve at the exit to a furnace is being investigated. The purpose of this new tapping technique is to regulate the flowrate of liquid furnace products( slags, metals and mattes). Numerical modelling and experimental work has been carried out on tapping of slags leaving a SIROSMELT reactor and the results found to be in good agreement. Numerical modelling has also enabled prediction of the important industrial conditions for the onset of blockage from the shape of the pressure versus flowrate curves. Slag launder experiments have been carried out and a one-dimensional heat transfer model was used to evaluate the effectiveness of launder covers and different coolants. From the experimental results and mathematical model some launder design guidelines such as inclination angle, covers and coolants have been developed.

Jan 1, 1991

By I. Gaballah

The kinetics of oxychlorination of pure CI-2O3 with C12+02 gas mixtures is studied by ThermoGravimetric Analysis (TGA) in non and isothermal conditions up to 1000 °C. The reaction of Cr2O3 with C12+O2 chlorination gas mixtures starts at about 550 °C and the reaction product is CrO2Cl2. The oxychlorination rate of Cr2O3 is almost proportional to the chlorine partial pressure and to the fourth root of the oxygen partial pressure in the chlorinating gas mixtures. At 800 °C, the maximum chlorination rate is obtained using a gas mixture having a C12/O2 ratio equal to 4. The apparent activation energy of the oxychlorination reaction of Cr2O3 is 87 and 46 kJ/mol at temperatures lower and higher than 650 °C, respectively. By varying the chlorine and the oxygen partial pressures of the oxychlorinating gas mixtures at temperatures higher than 550 °C, it is possible to extract selectively the chromium chlorinated compounds from the chromium bearing materials. a. Laboratoire Environnemem et Minéralurgie, BP 40, 54501 Vandceuvre, France, b. École Nationale Supérieure de Géologie, Rue du Doyen Marcel Rouhault, 54501 Vandoeuvre Cedex, France, c. Centre National de la Recherche Scientifique, 3 rue Michel - Ange, 75794 Paris Cedex, France, d. Insritut National Polytechnigne do Lorraine, Rue de la Font de Haye. 54501 Vandceuvre Cedex, France.

Jan 1, 1997

By Edgar E. Vidal

The deposition of ceramic materials onto substrates is of special interest in the development of surface related technologies. Research interest has been placed on using thermal plasma as the deposition method, specifically inductively coupled plasmas. Many different modifications to the same basic principle of deposition have been performed through out the materials research community. Such a technique may have many advantages over more conventional techniques, such as high deposition rates, high surface area coverage, clean energy source, no contamination from electrodes and operation near atmospheric pressures. Materials deposited vary from simple oxide systems like TiO2 to more complex structures like ternary oxides and nitrides. This paper reviews recent developments relative to the inductively coupled plasma deposition of thin films.

Jan 1, 2003

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

By M. A. Neri

A lead-free solder alloy Sn-57.5Bi-0.5Ag has been developed by mechanical alloying and foundry processes, and has great potential as a lead-free solder system, to low temperature applications. The mechanical alloying powders show a microstructure different to the microstructure obtained by the foundry process for the same alloy. Its melting point of 142°C is slightly higher than that of eutectic tin- bismuth solder. Examination of the microstructure revealed that eutectic microstructure is refined by the mechanical alloying process Ag additions. The lamellar structure of tin-bismuth gradually disappeared with the process of mechanical alloying, while intermetallic compounds AgaSn phase was formed. The Cu-Sn intermetallic compound layer formed at solder-copper interface is the Cu6Sn5 phase. Keywords: Lead-free solder, Microstructure. Mechanical alloying

Jan 1, 2003

By Derek J. Fray

"In order to extend the application of fused salts in\the electrowinning and electrorefining of metals, it is necessary to maximise the current density, minimise the voltage drop and greatly increase the area of electrode surface so as to compete with the space-time yield of pyrometallurgical reactions. The various designs of electrowinning cell are reviewed and it is shown that by the application of a modest centrifugal field it is possible to reduce the anode to cathode interelectrode spacing to 4 mm whilst still maintaining a current efficiency of 85-90%.The thermodynamic potential for electrorefining is far less than for electrowinning yet fused salt electrorefining is only applied in limited cases. The reasons for this are discussed and the important design parameters evaluated. It is concluded that by using packed bed electrodes, separated by a diaphragm, the possibility of electrorefining with very low energy consumption can be achieved. Carbothermically-produced metals are always cheaper than those produced by electrolysis but suffer from the disadvantage of low purity. It is proposed that fused salt electrorefining may offer an energy efficient way of upgrading the metal. IntroductionThe majority of metals can be deposited from fused salts (1,2) but as commercial production is restricted to the more reactive elements, it is worthwhile considering the advantages and disadvantages of fused salt electrolysis as' compared to smelting and aqueous electrolysis. The advantages over aqueous extraction are as follows:1) the much higher conductivities and diffusivities result in much lower IR losses and higher current densities can be achieved at modest voltages;2) the elevated temperatures of operation result in larger exchange currents which give rapid kinetics and lower activation polarisation for the electrode reactions;3) the absence of water as a solvent means that it is not necessary to consider the evolution of hydrogen as a competing cathodic reaction. Furthermore, alkali halide salts, often used as solvents in fused salt electrolytes, have high deposition potentials;4) molten salts generally are mutually soluble and, therefore, concentration polarisation effects are minimised."

Jan 1, 1988

By Rui-Qing Li, John G. Peacey, Peter J. Hancock

"Noranda has been investigating a pyrometallurgical process for the direct recovery of zinc from zinc concentrate and zinc and iron containing residues. The process consists of injecting dry zinc concentrate and secondary zinc materials into a molten iron oxysulphide bath, volatilizing metallic zinc into furnace off gas essentially free of sulphur or S02, fixing sulphur contained in the feed materials as iron oxysulphide matte which is disposed, and recovering metallic zinc in an ISP type lead splash condenser. Combustion of petroleum coke with air or oxygen enriched air inside the oxygen containing matte supplies part of the heat, and the products of combustion dilute the zinc-laden gas to a desired level.This paper describes the process concept, thermodynamic background, experimental tests, mass and heat balance calculation for a conceptual flowsheet, environmental stability of the residue and advantages and disadvantages of the process. Experimental tests have successfully proved the process concept and thermodynamic predictions. Direct smelting of zinc concentrate and residues inside an iron oxysulfide bath has a great potential to become a cost effective and flexible zinc smelting process.1. INTRODUCTIONZinc is mainly produced by a roast-leach-electrowinning process route, which accounts for about 80% of the world primary zinc production. This process produces high quality zinc with very high zinc recovery (>95%) but suffers from several major drawbacks such as using high cost electricity as reductant, producing environmentally problematic iron containing leach residue (jarosite or goethite) and the difficulty in treating secondary zinc feed materials containing high impurity levels, such as electric arc furnace dusts from the steel industry, and other complex sources. Also in some areas, markets for sulphuric acid are distant resulting in negative realizations on acid sales.The Imperial Smelting Furnace (ISF) process is the major pyrometallurgical process to treat zinc-lead concentrate. The advantage of this process over the electrolytic zinc process is its flexibility in treating high-lead, bulk concentrates with high recoveries of lead, copper and precious metals. However, this is a two-stage process involving sintering of Zn-Pb concentrates followed by blast furnace reduction. The process requires large amounts of high-quality coke which is a major operation cost, and the sintering process which results in serious environmental problems."

Jan 1, 1996