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By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By R. S. Celmer

The distributions of cobalt, molybdenum, copper, and selenium between nickel matte and silica-saturated iron silicate slag have been determined in the region of the metallic saturation boundary, at 1523 K. Results are given as a function of the composition of the coexisting Fe-Ni alloy and the activity of iron in the system. Under strongly reducing conditions, these minor elements display a marked preferential accumulation in the sulphide phase. It is shown that the dissolution of cobalt and molybdenum in slag follows an oxidative mechanism, and distribution equilibria are correlated with the oxygen potential. From these data, the thermodynamic properties of cobalt in nickel matte are computed. Further, comparisons of minor element partitions are made between the nickel and copper matte smelting cases under metal saturation conditions.

Jan 1, 1988

By G. Kyle Green

Zirconium chlorinator residues contain an array of rare earths, scandium, unreacted coke, and radioactive thorium and radium. Because of the radioactivity, the residues must be disposed in special waste containment facilities. As these sites become more congested, and with stricter environmental regulations, disposal of large volumes of wastes may become more difficult. To reduce the mass of disposed material, the U.S. Bureau of Mines (USBM) developed technology to recover rare earths, thorium and radium, and unreacted coke from these residues. This technology employs an HCl leach to solubilize over 99% of the scandium and thorium, and over 90% of the rare earths. The leach liquor is processed through several solvent extraction stages to selectively recover scandium, thorium, and rare earths. The leach residue is further leached with an organic acid to solubilize radium, thus allowing unreacted coke to be recycled to the chlorinator. The thorium and radium waste products, which comprise only 2.1% of the original residue mass, can then be sent to the radioactive waste facility.

Jan 1, 1995

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 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 Hu Long

In this, the first systematic study of the oxidation of orpiment (As2S3) in sulfuric acid solution under oxygen pressure at temperatures above 170°C, the effects of retention time, temperature, particle size, oxygen partial pressure, the concentration of sulfuric acid and pulp density were evaluated. The effects of cupric and ferric ions on the oxidation rate of As(III) to As(V) were also examined. The products of oxidation are As(III), As(V), SO42- and elemental sulfur. At temperatures ranging from 170 to 230°C, most of the arsenic was found to be in the trivalent state, and oxidation to As(V) with oxygen was very slow. This was confirmed by attempting to oxidize a synthetic arsenious solution. However, the rate of oxidation of As(III) to As(V) is rapid in the presence of ferric ion. Elemental sulfur was found at all temperatures investigated, which can be further oxidized to sulfate at high temperature.

Jan 1, 1999

The effect of change in slag composition upon metal losses to the slag and the relationship between slag composition and slag matte separation was investigated at 1400°C. The synthetic slags containing CaO, MgO, SiO2,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Precious Group Metals) from the Merensky Reef of South Africa. The matte with a grade of 9.3% Cu and 16.0% Ni was a typical electric furnace product. The results indicated that the Cu and Ni solubility in the slag increases with the increase of the basicity ratio and CaO and MgO contents of the slag. At constant CaO/MgO ratios the rise in basicity decreases the metal losses. When FeO and SiO2 contents of the slag are kept constant, the substitution of MgO with CaO decreases the metal losses. The relationship between slag composition and matte-slag separation was found to depend primarily on the basicity ratio and the FeO content of the slag. The net effect comes from a strong interaction of the two in such a way that increasing basicity and decreasing FeO contents deteriorate the clean separation of the two phases.

Jan 1, 1994

By Patrik Fredriksson

Thermodynamic data concerning FeO-containing slags is of importance in ladle refining of steel. With a view to generate a set of reliable and self-consistent thermodynamic data for these slags, experimental determination of the activities of FeO in binary and ternary slags was carried out using the gas equilibration method involving CO-C02-Ar gas mixtures at steelmaking temperatures. The slag samples in Pt crucibles were quenched after the equilibration and subjected to chemical analysis. The thermodynamic activities of "FeO" in the slags were calculated from the experimental data. The results are incorporated into a thermodynamic description of silicate melts in the present laboratory. The model is based on a Temkin-Lumsden approach and is able to compute the thermodynamics of higher order systems from the lower order ones.

Jan 1, 2003

By V. M. Paretsky

Oxygen-flame converting of a solid ground matte containing heavy non-ferrous metals in a wide range of concentrations is one of the perspective trends meeting the demands of modern non-ferrous metallurgy. As. a result, of semicommercial tests on oxygen-flame smelting of nickel matte containing 13,5-17,5% Ni; 0,45-0,65% Co under continuous autogenous conditions a converter matte containing 68 8-75,0% Ni and 0,48-1-,0% Co and ferrite -calcium slag containing 1,4-8,4 Ni and 0,16-0,56 Co were pro¬duced. Nickel recovery in a converter-matte was 76,2%, copper - 58,'2% and cobalt recovery in. a slag was 90%. Slag cleaning in an electric furnace allowed to after-recover nickel and cobalt in an alloy to produce a dumpy slag containing 0,03% Ni and 0,02% Co. The development of modern' ecologically pure energy-saving autogenous technologies of the treatment of sulphide raw materials containing heavy non-ferrous metals makes certain demands of the perfection of a process of converting rich sulphide-metallic intermediate products obtained at autogenous smelting. These-demands were connected first of all with the fact that converting process stages because of process periodicity are more unfavourable from the point of ecology, power intensity and unit stability. Besides, during rich matte treatment the problems connected with heat shortage when using air blast and heat excess-when using top oxygen blast to treat luquid matte a-rise and when enriching air blast by oxygen up to 26% fast erosion of the brickwork of a tuyere zone takes place. The technology of Outokumpu and Kennecott companies-on solid- copper matte converting in a flash smelting furnace using air blast is not universal as its possibilities are limited by certain composition of mattes. Besides, flash smelting to produce highly basic or combined slags requires larger enrichment-of blast by oxygen or extra fuel feed. Naturally a flowsheet with continuous converting of matte of various composition up to white matte production is simple,

Jan 1, 1993

By W. -S. Hwang, R. A. Stoehr, P. Ingerslev

"The flow of molten metal entering complex two-dimensional foundry molds has been modeled using the Simplified Marker and Cell (SMAC) and Solution Algorithm (SOLA) techniques. The molds were for a series of four and three-spoke wheel designs. The computer calculations were compared to physical experiments in which molten cast iron was poured into C02-bonded sand molds. The metal was photographed with a high speed motion picture camera focused through a Pyrex glass window on one face of the mold. To get good agreement between the calculations and the experiments, it was necessary to accurately represent the velocity through the ingate. This was calculated by application of the Bernoulli equation to flow through the feed system. Some difficulties were experienced with mathematical instability, expecially in the three-spoke design with a narrow ingate. This was overcome by using 100% upwind differencing, and over relaxation parameter near 1.0 (i.e. no over relaxation), and variable mesh spacing.IntroductionModeling the flow of molten metal entering molds has the potential for making significant contributions to the design of feed systems. It will supply information to the computer-aided-design systems of the future that will enable the designer to optimize the placement of gates, dimensioning of passages, and designation of casting speeds. Such design criteria have generally been based on application of energy balance (Bernoulli equation) principles to flow in the sprues, runners, and gates. Indeed, this is the easiest way to determine the proper dimensions to give a suitable filling time for a casting of a given size. A number of computer programs, including one by some of the present authors, have integrated such calculations into CAD systems. l Modeling the flow of metal inside the mold cavity requires other techniques that will handle free-surface transient flow. Stoehr and Hwang reported on the application of the Marker-and-Cell (MAC) technique to mold filling problems at the previous conference in this series at Hennicker, N.H. in 1983. 2 Although considerable progress has been made since that time in improving the accuracy, stability, and convenience of these techniques, the shapes to which they were applied remained limited. Also, physical verification of the results of the calculations was limited to water models.The work to be reported in this paper was undertaken with two objectives: (1) to apply these techniques to more complex and realistic shapes, and (2) to verify the results by comparison with flow patterns observed in molten metal poured into actual sand molds."

Jan 1, 1986

By William Petruk

A mineralogical and image analysis study was conducted on samples of U tailings from pilot-plant runs on Midwest ore in Northern Saskatchewan. The tailings had been subjected to simulated weathering for the equivalent of 10 years in a tailings facility (lysimeter). The pH varied from 7.0 at the beginning of the test to 5.9 at the end. The results show that during the simulated weathering sane of the gersdorffite, uraninite, galena and pyrite had oxidized, with gersdorffite being the most reactive and pyrite the least. Reaction was evident at the top of the lysilleter , but was most intense at the seepage discharge. sane of the released ions precipitated as Ni, Pb, and U arsenates, sulfarsenates, sulfates and oxides on particles of all minerals. Green crystals of Ni sulfate and white crystals of ca sulfate had precipitated at the surface of the lysilleter. Clay minerals and chlorite had washed from the top of the lysirneter towards the seepage discharge.

Jan 1, 1989

By K. Mansfield

Spent Pot Lining (SPL) is an unavoidable waste product of the electrolytic process in the smelting of aluminium. SPL is considered to be a hazardous waste in various countries because it contains significant quantities of absorbed fluorides along with traces of cyanide. In 1995, Portland Aluminium undertook the investment of AUD$26,400,000 to construct a Research and Development processing facility at Portland, Victoria, Australia, to treat SPL. Extensive research, development and design were carried out over 5 years prior to the investment decision. This study led Portland Aluminium to install an Ausmelt pyrometallurgical furnace to combust and melt the SPL producing a hydrogen fluoride (HF) laden gas, which was cooled and then converted to aluminium fluoride (AlF3). Both the cooling and AIF3 manufacture were processes developed by Portland Aluminium. Many commissioning, equipment reliability and process problems have been encountered that had not been experienced in the trials at Ausmelt or in the developmental process for the treatment of the furnace offgases to form AlF3. Designs based on anticipated process expectations have had to be re-engineered by the SPL team to ensure plant and operational success. In June 2001, the installation of the final major component - a slag granulation process - was completed. This has produced a vitrified (glassy) slag that is expected to have leachability qualities acceptable to the Victorian Environment Protection Authority (EPA) to allow commercial end uses of the slag material to be developed. Today (September 2001), the smelter has successfully used the fluoride product, namely 65- 70% AIF3, in aluminium production and the SPL plant has significantly increased throughput with expectations to be at annual design rates of 12,000 tonne of SPL in early 2002. "The Alcoa Portland SPL Process" has been technically developed and is a proven process for the treatment and recovery of valuable components from SPL materials.

Jan 1, 2002

By Hongli Wen, Guangkun Shen, Qiong Deng, Xuling Chen, Min Gan, Xiaohui Fan

"In this research, pyrite cinder which contains 53.51% Fe and 0.54% Pb was processed by magnetic roasting separation to obtain a concentrate with 64.62% Fe and 0.56% Pb. The concentrate was then leached with hydrochloric acid to remove lead. Several technological parameters which may influence the removal efficiency were investigated: the mass fraction of hydrochloric acid, pulp density, the leaching time and temperature. On the conditions that the mass fraction of hydrochloric acid of 5%, pulp density of 30%, the leaching time of 30 minutes and leaching temperature of20°C, the lead content in the concentrate was reduced to 0.19%. The product was suitable for agglomeration and pelletization. Through the analysis of the lead distribution and phase change during the whole process, the mechanism of lead separation from pyrite cinder was analyzed.IntroductionPyrite cinder is rich in iron, which defines its most extensive and effective use as raw materials for iron making. However, some pyrite cinders contain much non-ferrous metals, which is detrimental for the iron making process. Lead, one of the harmful elements, will destroy the blast furnace lining. Besides, it causes pollution of the environment[1]. Therefore it is necessary to remove excessive lead before entering the blast furnace. To separate the lead from pyrite cinder, much research was done, including flotation, high temperature evaporation and leaching. High temperature evaporation consumed too much energy. The flotation was difficult to obtain high- grade iron ore concentrate[2]. Majority of the leaching was direct leaching of pyrite cinder, which was also difficult to get high-grade iron ore concentrate[3]. This article explored the magnetic roasting method to get high-grade iron ore concentrate, acid leaching method of the concentrate to remove excessive lead, providing guidance for the efficient utilization of pyrite cinder."

Jan 1, 2013

By K. Narayana Swamy

Experimental results of 3-phase mixing in a physical model of a CCRL for metals refining, at high levels of bottom gas injection (up to a superfIcial gas velocity (Us) of 12.5 cm/min), are presented. A thermal tracer technique was used to elucidate both longitudinal mixing and interphase heat transfer. The results indicate that even under conditions of significant bottom gas injection, it should be possible to maintain acceptably low longitudinal mixing (D. < 20 cm2/s and D/uL < 0.1) in the CCRL. Interphase mass-transfer coefficients of the order of 0.02 cm/s and higher, are predicted from the measured interphase heat transfer coefficients using the mass and heat transfer analogy. Adequate performance is likely to be possible for an industrial CCRL, based on extrapolation of these results to full-scale conditions.

Jan 1, 1996

By Hong N. Vu, Jitka Jandova

"Gypsum and limestone methods were examined in this study to process zinnwaldite wastes originating from dressing Sn-W ores mined in the Czech Republic. These wastes containing 0.20-0.30% Li and 0.10-0.20% Rb were subjected to magnetic separation to obtain a zinnwaldite concentrate with 1.36% Li and 0.94% Rb. It was observed that processing of the zinnwaldite concentrate with gypsum resulted in almost 96% recovery of Li into aqueous liquors, whilst rubidium extraction was only 25%. At the same time, it is possible to extract almost 92% Li and Rb from the identical zinnwaldite concentrate if the concentrate is processed by limestone method. Lithium carbonate, a final product of both methods was recovered from the refined sulphate solution using K2CO3 as a precipitation agent and/or from unrefined hydroxide solution using gaseous CO2. In the continuation of this study, rubidium will be separated from carbonate solutions after Li2CO3 precipitation as RbAl(SO4)2, an intermediate for Rb2CO3 production. IntroductionLithium is used as an alloying constituent in lightweight alloys, as a heat transfer medium in nuclear reactors and as a component in primary and secondary batteries. With the development of a new generation of electric vehicles, the lithium demand will dramatically grow. Lithium chemicals find extensive application in many industrial branches such as metallurgical, glass, ceramic and pharmaceutical industries. Rubidium compounds are predominantly used in psychiatry and medicine, in magneto-optic modulators, solid-state lasers, phosphors and components of electrolytes for fuel cells. The four most important lithium minerals are amblygonite, spodumene, petalite, and lepidolite. Spodumene LiAlSi2O6 (6.0-7.5% Li2O) and petalite LiAlSi4O10 (3.5-4.5% Li2O) belong to aluminosilcate minerals. Lepidolite (Li.Al)3(Al.Si)4O10(F.OH)2 (3.30-7.74% Li2O), lithium mica, is the most important representative of the mica minerals, a subgroup of the aluminosilicates. It frequently contains 3–5% Rb2O and eventually caesium. Zinnwaldite, which has the general formula K(Li.Al.Fe)3(Al.Si)4O10(F.OH)2 (2-5% Li2O), is regarded as a variety of lepidolite with a high iron content. Commercial amblygonite is a complex phosphate (Li.Na)Al(F.OH)PO4 (up to 9.88% Li2O), however, its deposits have not been commercially exploited because of their small size. Natural brines with a high lithium chloride content are important in the industrial production of lithium [l]"

Jan 1, 2008

By Mukesh Jain

The liquor from potroom wet scrubbers is treated with lime to precipitate the soluble fluorides. The solids after filtration, referred to as scrubber mud, contain in addition to calcium fluoride, alumina, carbon, tars including polyaromatic hydrocarbons (PAH), cryolite and pachnolite and are considered hazardous. This communication deals with the pilot plant scale calcination of scrubber mud with a rotary kiln to obtain non-hazardous fluoride raw materials. Air classification was performed to separate the mudinto aluminarich andcalcium fluoride rich fractions which were then calcined. With proper control of calcination parameters and addition of lime, the carbon and tars were destroyed and hydrogen fluoride emissions were controlled. The calcined products could be used in the steel indusny as a fluxing agent or as a substitute for fluorspar in the production of aluminum fluoride.

Jan 1, 1994

By Tong Zhilin

The reasons why the pits were formed on the cathode in the process of Ni electrowinning and the methods how to prevent these pits from forming are described. Some examples are presented. It has &apos;been proven that P507 and P204 present in the electrolyte can effectively prevent pits from forming on the cathode.

Jan 1, 1993

By M. J. Adam

The U.S. Bureau of Mines has investigated the partitioning of complex minerals to simpler phases using sulfidation reactions for selective extraction of mineral values. This report describes research in which thermal processing of the complex Ti-bearing mineral ilmenite (FeTi03) resulted in partitioning of the valuable Ti metal to the simpler compound rutile (TiO2). Samples of ilmenite were blended with elemental S for thermal treatment at various temperatures under controlled atmospheres in an effort to dissociate the Fe from the ilmenite complex. Product characterization revealed that the Fe was partitioned &apos;from the ilmenite, forming a rim of pyrrhotite/pyrite (FeS/FeS2) on a rut il e core. The products were agate milled and then subjected to cursory magnetic and flotation techniques in an attempt to physically separate the partitioned phases. Partitioning results and phase concentration data are reported relative to thermal treatment variables and physical separation techniques.

Jan 1, 1991

By Saskia Duyvesteyn

Small ion-exchange resin particles provide faster mass transport than conventional-sized beads. Unfortunately, high pressures are needed to pump solutions through columns containing small resin particles. It is preferable to disperse fine resins in the solution being treated. Screens have been used to separate the resin from the solution, but screens do not retain fines created by attrition of the resin particles. We have developed a separation process based on flotation, which relies on the surface characteristics of the resin, instead of size. The resin is conditioned with a surfactant before dispersing it in the solution to be treated; this increases the hydrophobicity of the resin sufficiently for froth flotation, without introducing surfactant directly into the solution. The surfactant adsorbed on the resin surface does not appear to impair the kinetics of metal ion removal. A flowsheet for an effluent treatment process is proposed; other applications are clearly possible.

Jan 1, 1998

By Jagdish C. Agarwal

Although copper ranks very low in the order of abundance of elements in the crust of the earth, it has been one of the first metals utilized by mar, at his emergence from the Stone Age, about 10,000 years ago. Use of copper for weapons, tools, utensils and ornaments dates back to the twilight of history, 6,000-5,000 B.C. Native copper outcrops and the malleability of the metal explain its very early use by the cave-dwellers. The working, melting and extraction of copper from its minerals are among the oldest metallurgical achievements of the human race. The oldest complete smelting installations for the extraction of copper from its minerals, dated about the fourth millenium B.C., were recently discovered in the Timna Valley, Wadi Arabah, Israel. (1) The history of the developments of the extractive metallurgy of copper has been adequately reviewed recently. (2,3) The center of copper production migrated from the Eastern Mediterranean to Northern Europe (Mansfeld, Germany, Swansea, Wales) towards the end of the Middle Ages (1500 A.D.). The production of the metal was boosted tremendously in North America since the end of the nineteenth century (Fig. 1).

Jan 1, 1976