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By Robert H. Hsu

Palladium finely dispersed in a substrate of kieselguhr, Pd/k for short, has been successfully used for hydrogen storage, separation and pumping for a number of years at the Savannah River Site (SRS). Recently SRS has developed a new pd/k flow through bed (FTB) prototype for separating hydrogen from other gases and simultaneously storing the hydrogen on palladium. The FTB uses single-pass liquid nitrogen cooling during hydrogen absorption/separation/storage and electrical heating for desorption/unloading of hydrogen. Fourteen absorption-desorption or loading/unloading cycles using hydrogen have been conducted with the new FTB prototype. Test results show that all design performance objectives have been successfully achieved: recover 295% of hydrogen gas from feed gas, produce 99.9% hydrogen product gas and < 5% hydrogen in discharge gas. This paper will discuss characteristics of the palladium-coated kieselguhr or diatomaceous earth, design and operation of the FTB, and results of performance tests such as separation efficiency, hydrogen storage capacity and system heat transfer characteristics.

Jan 1, 2002

By Ch. -A. Gandin, M. Rappaz

"The grain selection mechanism which occurs during the growth of columnar dendritic structures is routinely used in the investment casting industry to produce directionally solidified (DS) and single crystal turbine blades. However, the evolution of the grain density with increasing distance from the chill has rarely been correlated with the evolution of the grain texture. This contribution presents a three-dimensional (3-D) stochastic modeling approach which permits the computation of grain maps, pole figures and grain density evolutions in DS superalloys. These predictions are compared with measurements resulting from an automatic indexing technique of Electron Back-Scattered diffraction Patterns. This 3-D stochastic model, which applies to uniform temperature situations, has to be extended to the dendritic growth in a thermal gradient. As a preliminary step, a 2-D Cellular Automaton (CA) has been coupled recently to Finite Element (FE) heat flow computations in order to predict the grain structures in complex shape investment cast part. The application of this CAFE model to the investment casting of a turbine blade is presented. Considering these results, the extension of the CAFE algorithm to three dimensions is discussed.INTRODUCTIONThe selection of columnar grains during the directional solidification of alloys plays a key role during the investment casting of directionally solidified (DS) and single crystal (SC) components for aerospace applications [I]. This selection mechanism, leading to a competition of the dendritic network propagation at grain boundaries, has been the subject of many investigations. In particular, the study of Walton and Chalmers [2] is remarkable since it provides a link between the evolutions of the density and of the texture of columnar grains with increasing distance from the mold wall. Since this original work of Walton and Chalmers, two new tools have become available, which enable one to revisit the problem of grain selection in much greater depth. The first one is a fully automatic indexing technique of Electron Back-Scattered diffraction Patterns (EBSPs) [3-6] which directly gives the crystallographic orientation of the solid at any location of the specimen. Pole figures, orientation distributions, misorientations between grains can be visualized very easily with this technique. This information can be directly compared with the results of a second tool: a three-dimensional (3-D) stochastic model (SM) describing the nucleation and growth of grains in a uniform temperature field [6-9]. In order to extend this model to non-uniform temperature situations, a preliminary 2-D model has been developed [10]. It is based on a Cellular Automaton (CA) algorithm coupled with Finite Element (FE) heat flow computations. Since the details of both the automatic indexing technique of EBSPs and the simulation tools have already been published [3-10], only a brief summary is given here."

Jan 1, 1994

By A. W. Bryson, K. C. Lenthall

"With the growth in the use of cobalt in industry, interest in its extraction and recovery has increased. With this increased interest comes the need for a fundamental knowledge of the processes involved in the recovery of cobalt metal. This paper examines the effects of cobalt concentration, catholyte pH, operating temperature and current density on cobalt electrowinning with respect to the current efficiency, cell potential and nature of the cobalt deposit. It is found that the cobalt concentration and catholyte pH affect the current efficiency, while current density and temperature affect the cell potential and thus the specific power consumption. Pitting on the deposit is affected by the catholyte pH and the operating temperature. Furthermore, the effect of feed flow-rate on catholyte pH, and thus current efficiency, is investigated. A model to predict the cell performance, which includes the flux of hydrogen ions through the diaphragm, is proposed.IntroductionCobalt metal is a silvery transitional metal found between nickel and iron on the periodic table. Due to its resistance to corrosion and other properties under high temperatures and its good work-hardening characteristics, it is favoured in alloys used in high temperature applications. These include aerospace, aircraft and high speed tools. Other applications include its use as a colourant in glass and ceramics, a drying agent in paints, a nutrient for livestock, a catalyst in the petroleum industry and, in the medical field, in prosthetics and radiology.The main deposits of cobalt are found in Central Africa, specifically Zaire and Zambia, although deposits also occur in Morocco, Canada and Australia. The cobalt is generally associated with other transitional metals including nickel, iron and copper. It is generally extracted by hydrometallurgical means and recovered from solution by electrowinning or hydrogen reduction. Little data [1-2] exists in literature on the electrowinning of cobalt from aqueous solutions. This paper investigates the effects of various operating conditions on the current efficiency, cell potential and deposit nature under continuous operation."

Jan 1, 1997

By D. A. Horne, V. R. Daiga

Certain steel mill wastes contain significant amounts of zinc oxide due to the use of galvanized scrap during the steel making process. Typically electric arc furnace (EAF), and basic oxygen process (BOP) flue dusts contain 20 to 30% zinc oxide and 40 to 50% iron oxides, along with smaller quantities of lead and cadmium. These materials can be recovered from the flue dusts by using a proven rotary hearth furnace (RHF) process. By-products of the recycling operation include a crude zinc oxide fume, which is captured in a baghouse filtering system, and sponge iron that may be recycled into the steel making operation. Crude zinc oxide properties plus the operating experience from two commercial RHF installations utilizing MR&E's DRyIron™ Process will be presented.

Jan 1, 2000

By Huang Kai

Uniform needle-like and spherical nickel oxalate particles were prepared by the chelating precipitation process, which was based on the reaction of oxalate acid and the solution of ammonia nickel chloride. The molar ratio of ammonia to nickel ion in the mixed solution is essential to determine whether the spherical or needle-like particles are formed, which means actually the concentration of ammonia is the key to determine the growth mechanism. When oxalate acid is added in the form of solid, it may act as the nucleation interface for the eariy-precipitated substance and so induce the formation of spherical particles. The PVP agent can improve the dispersing degree of the needle-like particles and higher reacting temperature leads to larger particles. The composition of the needle-like particle consists of ammonium and nickel oxalate instead of the pure nickel oxalate.

Jan 1, 2003

By D. Majuste

This paper describes an experimental approach to evaluate the effect of organic impurities or even additives on metal electrowinning and product quality. In addition to electrowinning tests and electrochemical measurements, the approach includes organic analysis by Fourier Transform Infrared spectroscopy and gas chromatography; video monitoring of the reaction interface; and product characterization by using scanning electron microscopy, crystallographic texture and bending tests. The mechanical behavior of metal cathodes was assessed with a customized bending device that is able to bend the cathodes up to angles similar to that of the stripping machine. In this work, the effect of a potential organic impurity, lubricating oil, on the production of electrolytic zinc is taken as a case study. The findings of the investigation allowed a better understanding on the role of this organic on energy consumption and product quality and a qualitative prediction for the behavior of Zn cathodes during the stripping operation. Simple control and optimization procedures resulted in significant energy savings.

By G. G. Richards

The zinc slag fuming process is used to recover zinc from molten iron-calcium silicate slags by treatment with pulverized coal and air. The rate of zinc fuming is controlled by the complex interaction of several kinetic factors including the rate of entrainment of coal in the slag, the extent of the coal-slag reaction and the rate of ferrous oxide oxidation to ferric oxide. This paper briefly outlines the mechanism of fuming and, on this basis, optimization of process parameters is discussed. Modelling analysis and recent industrial trials at Cominco show that coal entrainment in the slag, bath temperature, and bath depth are critical variables affecting process rate and efficiency. The first step in process optimization is to assess coal bypass of the bath. In general, changes which promote operation at a higher temperature, greater coal entrainment in the slag and extended residence time of the coal in the bath increase fuming performance. Coal entrainment is controlled by injection conditions whereas bath temperature is a function of coal combustion and ferrous oxide oxidation. Residence time of the coal is largely a function of bath depth. The implication of model predictions for continuous fuming is shown.

Jan 1, 1994

By Sudhir C. Dhara

An attempt has been made on the concentration of Platinum Group Metals (PGM) from the converter matte material by microbial .leaching. Biological oxidation of base metal sulfides such as iron, copper, nickel and free sulfur present in the matte material using Thiobacillus ferrooxidans is an alternative method to concentrate the PGM-and gold. The method which produces a platinum group metals concentrate is comparable to chemical processes and electrochemical process.

Jan 1, 1995

By Koji Matsubara, Yoshiaki Iguchi, Shoji Hayashi

Iron ore particles of a limonite iron ore were reduced completely with H2 at 1023K to 1273K in a fluidized bed. Then, at 973K, the formed iron was exposed to HrH2S mixtures (sulfur activity, as=0.5) for 3.6ks and carbidized with CO-H2-H2S· mixtures at 0.1 MPa. During the carbidization, the particles of about 150mg were sampled at every 600s interval. The sampled particles were analyzed by XRD and chemical analysis for C and S to evaluate the content of Fe3C, Fe5C2, Fe and free carbon. The reaction extent is defined as fo=Xfc3C +xFc5c2; x is the molar fraction of Fe in Fe3C. The carbidization curves can be fitted very well to -ln(l-f0)=g(pb T)t; g(p; T) is the carbidization rate, i.e. the carburization rate on the pore surface of reduced iron. The rate is found to be nearly proportional to the specific surface area of reduced iron, a P 0 , which decreases with increasing the reduction temperature. The value of a P 0 does not change by the carbidization and the stability of the iron carbide product in the atmosphere increases with the temperature.

Jan 1, 2000

By T. T. Chen

Canadian Electrolytic Zinc has developed the "cement-stabilization of jarosite residue" Garofix) process to stabilize zinc plant jarosite residues for disposal. The cement-jarosite mixtures cure quickly, have good mechanical strength and low hydraulic permeability; they possess good neutralizing capability and chemical stability. In the jarofix process, Portland cement partly decomposes jarosite to form (SO4MOH)12.nH2O, ferric hydroxide and an alkali sulphate. Approximately 40% of the jarosite reacts in mixtures containing 30% cement. The jarofix product also contains various Ca-Al-Fesilicate-sulphate-hydrate phases and gypsum, which bond the individual particles together imparting mechanical strength and reducing the permeability. Most of the reactions take place in the first few hours of curing. Ammonium jarosite is slightly more reactive than sodium jarosite but releases NH3 gas; water-soluble Zn in the jarosite residue is stabilized in the cement reaction products.

Jan 1, 1996

By M. Misra

The prediction and assessment of the reactivity of acid mine tailings has been a subject of numerous studies. The conventional approaches such as sulfur content, pH, net acid generating capacity and conductivity are used for assessing reactivity of the tailings. In this paper a new non-invasive Impedance Spectroscopy (IS) technique is used for the determination of reactivity and acid mine potential of tailings. This technique is also used to establish the long term stability and leaching propensity of the tailings agglomerated with alkaline binders.

Jan 1, 1994

By Jun Li

Rate processes of silver cyanidation were studied with the objective of understanding the reaction mechanism. The research was divided into three sections: anodic dissolution of silver in cyanide solutions, cathodic reduction of oxygen on silver surfaces and the direct leaching of silver in oxygenated cyanide solutions. The charge transfer steps plus the diffusion of reactants from bulk solutions to the silver surface were identified as rate-limiting and the rates of both anodic and cathodic reactions can be calculated using the Butler-Volmer equation and Fick&apos;s first law. Based on mixed potential theory and the results of electrochemical studies, a comparison of the rate obtained from direct leaching with that predicted from the calculation is made. Calculated results agree well with the experimental data.

Jan 1, 1992

By José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette&apos;s core. The measurement of the carbon content on the globules and the external iron layer is also presented.

Jan 1, 2003

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&apos; 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"&apos; 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 Jay S. Gunasekera

Metal parts are traditionally processed by either filly-liquid (e.g., casting) or filly-solid (e.g., forging) state. Semi-solid metal forming incorporates elements of both casting and forging. In 1991, Gunasekera(5) developed a model illustrating the influence of flow stress by the liquid fraction. The result fits Kiuchi&apos;s (1979)(7) experimental data quite well. This model assumed the liquid part is surrounded by solid as small pockets inside the material, which is opposite to the real practical situation. Since the melting usually first happens at the grain boundary, it is better to treat the semi-solid material as small metal crystal surrounded by liquid.

Jan 1, 1997

By C. Takano

The integrated iron and steelmaking industry generates large amounts and many types of solid dusts and sludge, at different phases of the production. Within these are: sludge of the Blast Furnace; coke fines; fine and coarse fractions from oxygen converters; sludge from water treatment at rolling mill unit; and others. In this paper the above dusts and sludge were physically and chemically characterized. The obtained results allowed defining self-reducing pellets using these materials. The high temperature behavior of the pellets were evaluated. Good results, with no decrepitation and swelling, and high yield of reduction, show that it is feasible to recycle them, as self-reducing pellets, in oxygen steelmaking converter.

Jan 1, 2001

By G. Diáz

A basic technology coping with a wide range of secondary zinc sources has been developed. The process combines an electrowinning stage, a solvent-extraction unit and a leaching procedure. The acidity generated in zinc electrowinning, transferred by the organic solvent to the aqueous raffinate, is reused to leach the zinc secondary materials. The basic process recovering zinc is described in detail. The route recovering other valuable metals such as copper, cadmium and lead associated with zinc is also described. This non-ferrous metals recovery route is advisable for either ecological and/or economical reasons. Main results of an experimental program aiming at the demonstration of the suitability of the process for several feed materials are summarized. Waelz oxides, galvanizing ashes and EAFD coming from different sources were tested in laboratory and continuous pilot plant campaigns. High zinc recovery, low reagents and utilities consumption, and effluents meeting environmental regulation were confirmed. The paper also includes the main results of a feasibility study of an industrial "base case". A mixed raw material and Spanish EAFD and 20,000 ta of zinc ingots production were chosen. The SGH zinc recovery from secondary raw material by means of the clean, safe and profitable Modified Zincex Process has been demonstrated. This reliable technology is ready for industrial application.

Jan 1, 1995

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

By M. P. Bohrer

A closed-loop hydrometallurgical process has been developed for treatment of smelter flue dust generated by copper recycling. The process is a semi-continuous operation in which zinc, iron, and copper are first extracted from the dust with a sulfuric acid solution. The lead and precious metals, initially present in the dust, remain as solids and can be recycled to the copper smelting furnace. Cementation with iron and zinc metal purifies the zinc and iron-rich liquid stream prior to spray drying. The spray-dried product, consisting of a mixture of zinc sulfate monohydrate and iron sulfate monohydrate, is a desirable micronutrient additive for use in animal feeds. Treatment of the smelter flue dust in this manner will generate a positive return on investment, as well as mitigate a potential environmental liability.

Jan 1, 1992

By Carlos Antonio da Silva

Steel refining reactors based on chemical heating are being used as an alternative to ladle furnaces, They show a high degree of flexibility in respect to heating rate in addition to carrying out refining reactions such as de-S, inclusion removal, alloying etc. IR-UT and CAS-OB are examples of such reactors. Their performance is dependent upon geometrical characteristics as well as operational conditions which determine the flow field inside the vessel. A physical model of the IR-UT process of the Companhia Siderúrgica de Tubarão, steel plant located in Serra, Espirito Santo, Brazil, was developed to assess the features of the flow field and its influence on the metallurgical behavior. Results of the physical model were used to optimize the process parameters in the industrial unit.

Jan 1, 2003