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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 M. D. Stephens

A new, one-step process for extracting titanium from titaniferrous materials has been demonstrated. In the process, depleted uranium tetrafluoride (DUF 4), a solid, is mixed with ilmenite (FeTi03) and heated to 900°C. Titanium is extracted in the vapor phase as titanium tetrafluoride (TiF4) and the DUF4 is converted to uranium-iron oxide. The process has been found to selectively fluorinate the titanium in ilmenite and is capable of producing high purity TiF 4 with very low iron content. TiF 4 can be collected by condensation or through reaction with a fluoride salt such as NH4F, KF, or NaF. The TiF4 produced from the process can be used to make titanium metal, titanium oxide, or fluorotitanate compounds. Since the fluorination process is highly selective for titanium, it avoids many of the separations and waste issues common to other titanium extraction processes.

Jan 1, 2001

By Konstantina Chalastara

Mixed phase titanium dioxide (TiO2) nanoparticles synthesized through hydrolysis of TiCl4 solution at different conditions, namely concentration, pH, and residence time are characterized and evaluated as photocatalysts. The process is operated in a continuous stirred-tank reactor, CSTR giving blends of anatase, brookite, and rutile nanoparticles that were further evaluated to find the optimum mixture for a photocatalytic sorption material. The titania nanoparticles are first characterized in terms of photocatalytic activity under UV light illumination using an organic model compound (methyl orange) and after that are tested for removal of toxic selenate and selenite species from simulated effluent waters.

By U .. C. Rojas, J .. C. Gomez

"Fire Refined Copper (EI Teniente Three Stars) has been produced at Caletones Smelter of Codelco Chile since almost the beginning of its operations.Due to changing features of the copper market, together with the targets on technical efficiency and productivity, it has become more and more relevant for copper industry to reach both, good final product quality and a proper environmental control.At present, copper refining process at Caletones Smelter takes place in two cylindrical tilting furnaces, where solid fluxes are injected through horizontal tuyeres into the molten bath. (Fig. N2 1)Solid reagents are pneumatically conveyed and injected into the liquid copper bath attaining excellent solid - liquid contact, so the impurities removal efficiencies are found to be high. Same injection tuyeres are used to introduce both oxidising agent (normal air) and reducing agent (reformed gas) into the molten bath. Air or nitrogen is used as conveying gas for solid reagents, depending on the process stage.This pap~r gives a fundamental description of the process and industrial results related to the injection of blend of sodium and calcium carbonates to remove arsenic and antimony, silica and granulated reverberatory slag to remove lead and a mixture of calcium carbonate and mineral coal to reduce the selenium content of the fire refined copper."

Jan 1, 1996

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

By Mojtaba Ahmadiantehrani

A previous study showed that up to 80% gold extraction could be obtained with 160 lbs/ton hypochlorite consumption at ambient temperature from a low grade Carlin-type carbonaceous ore. Crushing the ore to a finer size and agglomerating with cement decreases hypochlorite consumption by 60%; while, agglomeration and curing the cement-ore mixture with hypochlorite solution has no significant effect on total gold extraction. The high hypochlorite consumption is due to oxygen depletion as the solution percolates through the column, i.e., oxidation of gangue materials. These side reactions are reduced at sub-ambient temperatures resulting in a substantial further decrease in hypochlorite consumption. The optimum temperature range and additional reduction of hypochlorite consumption by introducing the reagent into the column at different elevations will be discussed.

Jan 1, 1992

By B. Q. Li, Y. Shu, K Lynn

"This paper discusses the effects of magnetic field and internal radiation on the melt flow and solidification morphology during solidification processing of oxide crystals for optoelectronic and remote sensing applications. The numerical solution of the integral differential equation characterizing the internal radiation and the magnetohydrodynamic equations describing the magnetic and transport phenomena is obtained by applying the combined discontinuous and continuous finite element method. The results show that both internal radiation and an externally applied magnetic field can have important effects on the melt flow and solidification behavior during the melt processing of oxide materials.IntroductionOptical single crystals are widely used in optical and electronic devices. These crystals are often grown from high temperature oxide melts under strictly controlled conditions. As in the well-known single crystal growth processes for semiconductor wafers, thermal gradient in the melt is a major contributing fuctor to the oxide melt pool. Unlike the semiconductor single crystal growth processes, however, the oxide melt is semitransparent and internal thermal radiation plays an important role in redistributing the thermal energy in the melt pool. Our recent experience with pilot-scale plant measurements also shows that the oxide melt is electrically conducting, although its electrical conductivity is considered much lower than the liquid metal or semiconductor melt.The fact that the oxide melt is absorbing and emitting in the thermal radiation frequency range makes it difficult to study the thermal energy transport in the melt pool. This is because thermal radiation is governed by a hyperbolic differential equation, which is different from those describing the transport processes in liquids. Also, our understanding of how thermal radiation interacts with other transport mechanisms such as convection and conduction is rather limited at point in time, in particular in high temperature oxide melts for optical single crystal processing."

Jan 1, 2004

By Charles L. Richman

The effect of the addition of Silver Sulfide on the rate of Chalcopyrite (CP) of Sulfuric acid (H2SD4 leaching is discussed, Although Ag2S in an expensive addition, a theoretical explanation of it's use will aid in the development of a economic substitution. We have used cyclic voltammography to show the presence reaction species at different potentials. Cyclic Voltammography maps the surface reaction current peaks on CP, to regions on the CP Phorbaix diagram. AC Electro-lmpedance spectroscopy (EIS) models the surface impedance properties, which control the rate of electron and ion transfer, and the surface kinetic reactions, with and with out light. EIS and other measurements show that AgCuS u Photo-reactive material- The EIS results are compared with the SEM and EDXA results to show the presence of diffusion pores, and diffusion controlled reactions during CP leaching without the addition of silver sulfate. We hypothesize that AgCuS is an ionic conductor like Ag2S. EIS shows an imposed negative leaching rate greatly. Our theory shows how the formation of Silver Copper (1) sulfide layer at open circuit potential gives an effect similar to negative potential, that is enhanced with illumination. We verify that AgCuAS is an N-type semiconductor that forms a diode type junction with the electrolyte with the Mott-Schoottly relation.

Jan 1, 2001

By Arpad E. Tonna

Recycling of materials from lithium-oxyhalide batteries is a complex task, since the dismantling of batteries is associated with many hazards. The electrolyte and the lithium anode metal are extremely reactive in the presence of water or water vapor. Therefore, the dismantling process is a complex task. In this process, the lithium battery is electrically discharged, then frozen in liquid argon, and cut into small size pieces. These are fed into an incinerator, where the unreacted portion of lithium metal, thionyl chloride, plastic separators and carbon paste are decomposed and burned to gaseous products. The aluminum, iron (steel) and nickel pieces are recovered as saleable scrap metals. The off-gases are scrubbed with an alkaline sodium carbonate containing solution. The clean gases are released to the environment. The particulate mater recovered from the scrub-suspension would be available as additive to the cement industry . The recycling of battery decomposition products improves the economic viability of the disposal processes. Work is in progress to develop safe handling, processing and recycling large size lithium batteries.

Jan 1, 1995

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By C. Lupi

"The energy consumption of copper production by electrowinning, generally represents more than 1/4 of the total energy requirement in hydrometallurgical traditional process (roasting, leaching, purification and electrowinning). The considerable saving can be achieved just in this step that requires about 2.2 kWhlkg of the produced copper. To save energy the cell voltage, or more appropriately its anodic component, can be reduced: that is because the anodic voltage represents the main component of cell voltage and so it is largely responsible for the excessive energy consumption in copper sulphate electrowinning.In this work some ways are studied to lower the anodic voltage. First the cobalt ions were added to the sulphate solution in order to study the catalytic effect on oxygen discharge. Then lead alloys anodes (Pb-Ag, Pb-Sb-Ag and Pb-Ca) were used to promote a better oxygen evolution as a result of a different anodic surface. Their behaviour was compared with the PbSb traditional ones. Finally, as already pointed out by several authors for zinc electrowinning, ethylene glycol was employed as anodic depolariser in order to verify its effectiveness in the case of copper electrowinning. By combining all the above-mentioned ways, energy saving ranging from 20% to 27% is achieved.All the tests were carried out on a laboratory pilot-plant for long time to simulate the industrial conditions. The obtained copper deposits were observed by SEM to highlight their morphology."

Jan 1, 1997

A novel pressure leaching process for platinum group metal (PGM) feedstocks is described. The process is particularly well suited for treatment of ores or concentrates that are too low grade for economic processing by the conventional smelting/leaching process. Operating conditions have been identified under which gold, the PGM's and the base metals dissolve simultaneously in a pressure leaching autoclave. The product of this leaching process can then be treated by one of several flowsheets, of which the preferred will likely involve solid/liquid separation, followed by precipitation (or adsorption on activated carbon) of gold and the PGM's, followed by copper solvent extraction/electrowinning. Depending on the concentrations of nickel and cobalt, the copper raffinate would either be partially recycled to the autoclave to allow NilCo concentrations to build up, or it would proceed directly to a Ni/Co refinery. This paper deals with the pressure leaching process and the recovery of gold and the PGM's from the pressure leach product.

Jan 1, 2000

By Vinod K. Sikka, René Cooper

"Cohoes, New York 12047 Intermetallics are an attractive class of advanced materials. The aluminide intermetallics offer advantages including: (1) lower density, (2) oxidation resistance, (3) carburization resistance, and (4) interesting mechanical properties because of their ordered crystal structure. Even though the attractive properties of the aluminides and other intermetallics have been known for nearly four decades, their practical applications have not been developed for two reasons: (1) the poor ductility (in some cases, both ambient and high temperatures) and (2) the lack of processability into meaningful components. Recent advances such as ductilization of Ni3Al by small additions of boron and the knowledge that environmental effects are the major cause of poor ductility in Fe3Al and FeAl systems have brought the intelmetallics into the forefront of research and their commercial applications. This paper has described a method for melting Ni3AI-based alloys that successfully utilize the exotherrn for the formation of NiAl from the elemental materials. The reaction-synthesis method has also been utilized for the production of NiAI and NiAI-based alloy powders from the elemental powders. The reaction-synthesized powders of NiAI and NiAI-based alloys were consolidated by hot extrusion and evaluated for tensile properties over a temperature range from room temperature to 1050ºC. The powder-processing conditions have been found to have more influence on the ductile-to-brittle transition temperature of NiAI than the powder-production method.IntroductionIntermetallics are an attractive class of advanced materials [1-11]. The alum in ide interrnetallics offer advantages including: (1) lower density, (2) oxidation resistance, (3) carburization resistance, and (4) interesting mechanical properties because of their ordered crystal structure. Even though the attractive properties of the aluminides and other interrnetallics have been known for nearly four decades, their practical applications have not been developed for two reasons: (I) the poor ductility (in some cases, both ambient and high temperatures) and (2) the lack of processability into meaningful components. Recent advances such as ductilization of Ni3Al by small additions of boron and the knowledge that environmental effects are the major cause of poor ductility in Fe3Al and FeAl systems have brought the intermetallics into the forefront of research and their commercial applications. The paper will briefly review the processing techniques being pursued for the commercial applications of Ni3Al-based intermetallics. The major emphasis of the paper will deal with synthesis of Ni3Al and NiAI intelmetallics."

Jan 1, 1994

By J. L. Holman

The Bureau of Mines is investigating recovery of Ni, Co, Cr, and other metals from mixed contaminated supera110y scrap. The scrap is melt-refined and cast into anodes for electrodeposition of recyclable Ni-Co alloy. Melt oxidation using roasted superalloy grinding sludge as oxygen source can divert the Cr to the slag but with excessive Ni-Co loss. Melt oxidation-carburization or direct melt carburization retains -95 pct of the Ni-Co in the anode alloy. With direct carburization, -90 pct or more of the Cr and other refractory metals report to the anode alloy, largely as carbide phases insoluble in electrolysis. Electrorefining data relate parameters such as controlled cathode potential, Fe and Cr impurities, pH, and compartmented cell use, to current efficiency and Ni-Co deposit quality. Recovery of -90 pct of the Ni-Co in the scrap can be achieved. Preliminary experiments to recover Cr, W, and other metals from the anode sludge and other byproducts are discussed. 347

Jan 1, 1987

By Fathi Habashi

Nitric Acid has been used for over 50 years in the uranium industry and in phosphate fertilizer manufacture. Its application in the treatment of sulfide concentrates is relatively recent. A review of recent developments is given.

Jan 1, 1999

By René Winand

Due to chemical and electrochemical behavior of the most common additives in copper electrorefining i.e. gelatine, thiourea and chloride ions, it is essential to simulate as far as possible true industrial practice while performing laboratory experiments. The three additives must be studied simultaneously, and added continuously to the electrorefining cell. Ratio electrolyte volume to cathode area; ratio bleed flow to cathode area; hydrodynamic conditions; residence time of electrolyte in the cell; current density; electrolyte and soluble anode must be as near as possible to industrial ones. Experiments performed in the author's laboratory show that under these conditions, reproducible results can be obtained at normal industrial current density and at high current density as well. Problems are however still encountered when developing a sensor for additives monitoring, due to electrolyte redox potential and to substrate influenced thin layer deposition.

Jan 1, 1995

By May Nyman

Due to the vast diversity of chemical media in which metal separations are executed, a wide range of ion separation materials are employed, This ,results in an ongoing effort to discover new phases with novel ion exchange properties. We present here the synthesis of a novel class at, thermally and chemically stable microporous, niobate-based materials. Ion exchange studies show these new phases are highly selective for Sr2+ and other bivalent metals.

Jan 1, 1999

By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

By A. V. Reddy, C. Beckermann

"The DC continuous casting of a grain refined AI-4.5%Cu round ingot with realistic boundary conditions is numerically simulated. Of particular interest are the effects of the transport of free solid in the form of equiaxed grains on the macro segregation patterns and the final grain size distribution. The study uses a previously developed two-phase model that incorporates descriptions of heat transfer, solute redistribution, melt convection, and solid transport on the system scale with microscopic models of solutal undercooling, microsegregation and grain impingement. The numerical results indicate that grain transport inhibits the formation of inverse segregation in the ingot shell and promotes negative centerline segregation. This is explained by the reduction in the solid coherency next to the mold and the advection of solute-lean grains towards the centerline. Comparisons with the experiments of Finn et al. [5] illustrate the need for considerable improvements in the model. IntroductionMacrosegregation continues to be one of the concerns in DC continuous casting of aluminum ingots. The variation in composition over the ingot cross section results in the need to adjust alloy composition in order to meet mechanical property specifications in finished products. The extent of macrosegregation is greatly affected by the casting conditions, such as casting speed, superheat, cooling rate, mold size, alloy composition, and grain refining practices. Thus, it is of great interest to develop a comprehensive mathematical model to simulate the casting process, enabling the selection of conditions that minimize macrosegregation while maintaining a high productivity."

Jan 1, 1994

By den Bulck A. Van

In Europe, 50% of the copper originates from recycling. High-Cu containing scraps are regularly rich in impurities like Fe, Ni, Sn and Pb. Many high-Cu containing scraps are fed directly into anode-furnace casting installations or furnaces with limited refining capability. The impurities levels of the anodes produced in these processes should however remain acceptable for further electro-refining. The distribution of Sn between copper and slag has been investigated for conditions relevant to copper converting. Unlike previous studies, this work focuses on the behavior of Sn relevant to fire refining conditions, which are essential for anode refineries.In this study, liquid Cu–1Sn and CuOx–FeOy–SiO2 slag, with CaO additions, were equilibrated at 1300 °C in vacuum sealed SiO2 ampoules. After metal–slag equilibration, the samples were quenched in water. The composition of the slag and Cu metal was investigated with Electron Probe X-ray Microanalysis. The distribution coefficients of Sn between slag and Cu metal were determined as a function of slag composition.