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By Neil E. Ryan

Because of their chemical reactivity and affinity for oxygen, rare-earth elements are difficult to extract, and due to their close chemical similarity, it is an exacting task to separate one from the other. Nevertheless, these same characteristics can be used to benefit other metals by enhancing their resistance to high-temperture oxidation/corrosion and by inhibiting their corrosion in aqueous environments. This paper gives an overview of the use of rare-earths: [a] as alloy additions, [b] in coatings, and [c] when added to hostile environments, to retard rates of high- temperature oxidation and inhibit aqueous corrosion.

Jan 1, 1992

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts, The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10-7 atm. The concentration of CU2+ in such slags becomes significant at oxygen potentials of greater than 10-7 atm at 1300 °C. The activities of CuO0.5 and AsO1.5 in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of SiO2 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2x 103 cm2/s at 1350 °C and activation energy of 16 kcal/mol. Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300°C. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material,

Jan 1, 2003

By Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn't significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By Wang Zhi

High-Mg-content concentrates are usually treated in Jinchuan flash smelting Furnace. Because the viscosities of high-Mg-content slag is very high, the operation of flash smelting becomes very difficult. To solve this problem, the viscosities of the semi-synthesized FeO-MgO-Si02 slag of different compositions were measured. The results showed that when in the slag the weight percentage of MgO [m(Mgo)] is 6-10%, the ratio of the weight percentage of iron to that of Si02, m(Fe)/m(SiO2) is 1.1-1.4 and the temperatures are within 1473?1773K, the slag viscosities increased with the increase of m(Mgo) and m(Fe)/m(sio,). When m(Mgo)<6%, the smelting temperature should be controlled at I 300°C in order to to keep the smooth operation. When m(Mgo» 10%, the temperature should be kept above 1633K. When the content of MgO is higher, a lower viscosity slag ean be produced by decreasing the ratio of m(Fe)/m(sio,). The appropriate ratio of m(Fe)/m(sio,) for Jinchuan flash smelting furnace is about 1.2.

Jan 1, 2003

By Finlay Campbell

Nickel laterite pressure acid leach plants and reduction roast plants have had a checkered history in their engineering, construction, startup and operational reliability. Many potential projects have been the subject of detailed studies over the last thirty to forty years but relatively few have advanced to commercial production. Four reduction roast plants are currently operating, an additional one was partially constructed but never completed, and another was started up in 1974 and shut down after 12 years operation. Three acid leach plants have been built and commissioned in the last five years, trying to follow the example of the Moa Nickel plant in Cuba. An additional acid leach plant project is currently on hold, following limited construction work, its future subject to review by the owner because of potential cost over-runs. This paper attempts to discuss difficulties that may be encountered as a project is developed and will address factors which may affect production ramp-up schedule, long term production performance and overall production success. Comparisons are made with ramp-up performance at other large metallurgical plants that employ some comparable unit operations. Keywords: Caron, PAL, nickel laterite ore, ramp-up, reliability, process development, equipment design, step-out, commissioning, startup.

Jan 1, 2004

By Mitsutaka Hino

The contents of gangue minerals, such as A1203, P205, crystalline water and so forth in the iron ore imported to Japan tend to increase year by year, Though the increments of such gangue contents are approximately 0.1-0.2 mass%, some problems for the blast furnace operation in ironmaking process have already been reported, In order to clarify the mechanism of harmful effect caused by the small increment of gangue minerals, mainly A1203, on the blast furnace operation, the dripping behavior of FetO-CaO-SiO2-AI2O3-MgO slag from the iron funnel, which simulated the micro-porosity in sinter ore, has been observed with the wide range of basicity, Al2O3, FetO and Mgo contents. The effect of MgO on the dripping behavior of slag has been summarized in this paper, It was found that the addition of 2mass% MgO resulted in large increase of hold-up on the most of the conditions. When FetO content was less than 20mass% and the basicity was lower than 0.8, MgO lowered the hold-up even if the slag contained 10mass% Al2O3. Every slag hold-up showed the minimum at the basicity of less than unity on the conditions of constant FetO and A1203 contents. This trend became remarkable when the slag contained 2 mass% MgO.

Jan 1, 2003

By R. Burkhard

Recovery of metals from complex mixed wastes is a challenging task of modem material and waste management strategies. Thermal methods are an important tool in this respect. Plasma turned out to be particularly useful for treatment of complex or toxic wastes and residuals. In order to study plasma processes at reasonable costs, a pilot plasma plant has been used and wastes like ~pent Raney-Nickel catalysts, copper and ah.:lminum drosses, and. other metal containing wastes were investigated. The paper summarizes the most significant findings

Jan 1, 1995

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By Fiseha Tesfaye, Pekka Taskinen

"Thermodynamics of the equilibrium phase assemblage Ago_9Cul.lS-Cu2-xS-CuS have been studied by an EMF -method. The ternary phase was synthesized from the pure Cu2S and Ag2S in vacuum furnace at high-temperature and mixed with appropriate compositions of Cu2S and CuS to form the cathode electrode. The EMF-measurements were made on the solid-state galvanic cell Pt(-) I Ag I RbAg,ils I Ago9Cu1.1S-Cu2-xS-CuS I Pt(+), in a temperature range from 316 K to 498K.Based on the measured EMF vs. T relations, thermodynamic functions (?fG° , ?fS and ?fH°) of stromeyerite (Ag0.9Cu1.1S) in equilibrium with Cu2-xS and CuS have been determined. The obtained experimental values have been compared with the available literature values. New experimentally determined thermodynamic properties of the solid solution (Ag,Cu)2Sss were determined.IntroductionDue to intense mining of high grade sulfide ore minerals in the past, recently, the available sulfide ores are poor in metals and becoming increasingly complex; such that, the production of high grade metals by the conventional pyrometallurgical processes is compromised. Consequently, smelters are in need to modify their operating flow sheets and strategies for processing more complex feed materials economically, while meeting the strict environmental regulations. To make the appropriate modifications, accurate thermochemical data of phases and phase assemblages which exist in these complex ore minerals are essential.Silver-bearing sulfosalts are encountered in ore minerals for the production of base metals and are common sources of silver. Among the silver-based sulfosalts, stromeyerite (Ag0_9Cu1.1S) is relatively common ore mineral in most hydrothermal vein and replacement deposits [1]. Recently, the ternary chalcogenide compound Ago0.93Cu1,07S has been studied, intensively, due to its high ionic conductivity and gradual disorder in the sequential phase transitions [2]. Therefore, accurate knowledge of the thermodynamic properties of stromeyerite has considerable fundamental and practical interest in many aspects of extractive, chemical and physical metallurgy."

Jan 1, 2014

By Jorge A. S. Tenorio, Chuanwei Zhuo, Joner O. Alves, Yiannis A. Levendis

"Reduction of combustion-emitted greenhouse gases, which are associated with global warming, may be achieved by use of CO2-neutral alternative fuels, such as bio-ethanol. Distillers Dried Grains with Solubles (DDGS) are the main co-products of the com-grain-based ethanol industries. In 2009, the North American production of ethanol from com was about 38 billion liters, which generated approximately 31.5 million tons of DDGS. Samples of DDGS were pyrolysed at temperatures of 600-1000 °C in a two-stage laminar-flow horizontal furnace, and a catalyst system was used to synthesize nanomaterials. This work presents a microstructural characterization of these nanomaterials by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Results showed that the nanomaterials produced from pyrolysis of DDGS were in the form of long, entangled, rope-like structures with rugged walls, lengths in the tens of microns, and axially non-uniform diameters in the range of 100-300 nm.IntroductionThe interest in ethanol has increased considerably worldwide due to the necessity of finding renewable and cleaner energy resources [1, 2]. According to the Renewable Fuels Association (RF A), the world ethanol production in 2008 was approximately 65.7 billion liters (17.3 billion gallons), which figure represented a 24% increase in the production over that in the previous year [3]. The major producers of ethanol are the USA and Brazil, which together account for 90% of world production. The main feedstock for ethanol in USA is com grain, whereas sugarcane predominates in Brazil [2-4]."

Jan 1, 2011

By Ali Hasham

Reduction rates of FeO in CaO-SiO2-Al2O3 slags by Fe-C melts have been investigated experimentally at 1723 K. The rates were estimated using experimentally determined CO(g) evolution rates. Flash X-ray images were employed to visualize the behavior of the melt-slag interface during the reactions. The influence of melt interface was examined by conducting two types of experiments - (i) dropping one (or several) Fe-C droplet(s) weighing 2 g into the molten slag bath, and (ii) dropping a small amount (10-30 g) of slag onto a Fe-C melt weighing 400 g. The rates from both types of experiments were compared and analyzed to determine the rate limiting steps. It was established that neither the carbon transport in the Fe-C melt, nor the transport of gas species in the gas film adjacent to Fe-C melt was responsible in limiting the reaction rate. It is possible that the slag phase mass transport may be controlling the initial reduction rate in the droplet experiments. However, a, different mechanism was responsible in limiting the reduction reaction when the overall %C in the droplets fell to about 2-3.

Jan 1, 1992

By Jerry D. St. Clair

A multidisciplinary team of scientists and engineers at Wont has been working to understand heavy metal contamination of DuPont process waste streams and technologies for abatement of these metals. As part of this effort, an extensive study was made of a specific waste stream of importance in DuPont&apos;s environmental commitment. This 200 gpm stream contains 5-5000 ppm of nickel plus a variety of inorganic and organic constituents. The chemical complexity of the waste rendered conventional. alkaline precipitation ineffective, and only through the simultaneous application of analytical characterization, fundamental chemical understanding, and process engineering did effective technical approaches emerge. In this instance, ion exchange, sulfide precipitation, and caustic digestion ultimately proved successful in reducing the nickel to below the 1 ppm target. The results of this study will be presented, along with key learnings about the process of solving heavy metal contamination problems.

Jan 1, 1994

By Toshiki Kabutomori

In fuel cell powered automobiles, hydrogen is required to be stored in materials that have a hydrogen storage density of over 4 mass%; further, these materials should be capable of supplying hydrogen by using the waste heat from a fuel cell, which is at a temperature of 373 K, in order to match the mileage of gasoline-powered vehicles. A Ti-Cr-V alloy, which exhibits a BCC structure and forms a solid solution, is a promising candidate for onboard hydrogen storage materials. Although it has a large hydrogen storage capacity of over 3.9 mass%, the rechargeable hydrogen capacity is limited to approximately 2.6 mass%. In this study, the effects of fine pulverization of the alloy on PCT (hydrogen pressure-composition-isotherm) characteristics were investigated in order to improve the rechargeable hydrogen storage capacity of the alloy. From the PCT measurements of the finely pulverized samples of the alloy, a plateau in the absorption curve was observed to begin at a hydrogen concentration of 0.5 mass%; further, a rechargeable hydrogen storage capacity of 3.3 mass% was obtained. This was greater than that obtained from the sample that was not finely pulverized, i.e., 2.5 mass%. However, the plateau width in the desorption curve was 2.5 mass%, which was the same as that observed for the sample that was not finely pulverized. The increase in the rechargeable hydrogen capacity during absorption is attributed to the precipitation of the -hydride phase (MH~2) directly from the metal phase (phase). The precipitation of the phase (MH~0.5), which should be formed in low hydrogen concentrations, is suppressed as a result of a possible reduction in the internal defects such as dislocations, vacancies, and grain boundaries by fine pulverization and annealing of the alloy.

Jan 1, 2006

By Zbigniew Zurecki

The selection of atmosphere composition is critical for controlling surface quality of reactive aluminum alloys during solution treatments. An improper selection of annealing atmosphere can result in surface blistering in AI-Mg and sub-surface depletion of lithium in AI-U ingots. To determine optimum atmosphere compositions for homogenizing A1-Mg and Al-Li alloys, Ii number of exploratory experiments were carried out in air, nitrogen, and carbon dioxide based atmospheres including reactive impurities or additive such as moisture and sulfur hexafluoride. This paper describes the influence of these atmospheres on high-temperature oxidation and sub-surface defects. The results are discussed in terms of the change in Pilling-Bedworth ratio.

Jan 1, 1996

By W. G. Davenport

A flash furnace can be run many different ways. It can, for example, be operated with: (a) highly 02"enriched, ambient temperature blast and no fossil fuel (b) considerable fossil fuel and hot, slightly Or enriched blast. It can also produce different grades of matte. With all these possibilities, the flash furnace operator can benefit from any technique that will indicate the &apos;best&apos; way to operate his furnace. One such technique is Excel&apos;s &apos;Solver&apos;optimizationroutine#. This chapter shows how our matrices and Excers optimization.abllity can be used to optimize a flash furnace operation. The chapter sets three optimization goals: (a) minimum industrial oxygen + oil cost, $ per tonne of concentrate (b) maximum smelting rate, tonnes of concentrate per hour (c) maximum profit, $ per hour.

Jan 1, 2001

By J. Bostjancic

As wastewater discharge regulations become more stringent, power plants, manufacturing plants and other industrial sites are looking for ways to reduce makeup water requirements and to recycle and reuse as much wastewater as possible. In some cases, environmental regulations require zero liquid discharge, meaning all wastewater must either be retained on site or reduced to solids for disposal off site. Zero liquid discharge or "closed-loop" wastewater treatment systems using evaporators and other process equipment have been well-accepted in recent years. Often overlooked is the fact that zero discharge is not just the latest fashion--many commercial zero liquid discharge systems have been in operation since the mid-70&apos;s. This paper will give specific examples of zero liquid discharge operations from 1974 to the present, showing how evaporation equipment and processes have changed to meet the requirements of industry and environmental regulations.

Jan 1, 1996

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

By Carla Lupi

NiMH sealed cells (portable cells) are today widely used in all consumer applications replacing primary alkaline batteries: wireless mobile communication, portable computers and camcorders, are the largest application segments. The Italian market. of NiMH cells is steadily growing, following the impressive penetration rate of the cellular phones. The organization of a national collecting system and correct recycling process are the key factors to prevent environmental impact associated to these wastes, while the metal values recovery can improve the feasibility of the recycling process The University of Rome, Texeco Engineering S.d, and MO.SMO.DE. S.a.s. have developed a combination of mechanical and hydrometallurgical processing to recover Nickel, and Cobalt salable products and rare earths intermediate products. A new plant located in South Italy, designed after this technology, is able to recycle waste Ni-MH batteries collected in the Italian territory, together with other industrial and portable batteries based on different chemistries. The process is able to treat both individual cells and plastic power packs and includes as basic steps an original crushing and elutriation treatment to separate plastic, metallics, and active mass components that are subsequently treated by a hydrometallurgical process to recover Ni, Co, and RE. The hydro metallurgical main steps are: acidic leaching, RE separation, multistage precipitation of Ni, Co and Fe and final solvent extraction on dissolved Ni and Co salts. For each operation the operative condition have been determined.

Jan 1, 2000

By Józef Czemecki

Polish copper concentrates are characterized by high levels of impurities, particularly Pb and As. Two technologies are being used for copper concentrate smelting at KGHM Polska Meidz S.A., namely the shaft furnace process (Legnica Copper Smelter, Glogów I Copper Smelter) and a single-stage process for direct to blister concentrate smelting in a flash furnace (Glogów II Copper Smelter). Both technologies are used at different physical and chemical conditions which results, in different impurities behavior. The paper presents flow sheets for copper production in a plant using the shaft furnace process and in another in which a single stage flash process is used. The metals distribution in particular semi-products is given as well as a method for elimination of impurities from the copper production cycle. Methods are also discussed for alloy and matte converting and copper refining to obtain low Pb and As concentrations in anode copper (0.3% Pb and 1500 ppm As maximum) that are being used in the KGHM Polska Meidz plants. Useful co-operation between the plants using different technologies, aimed at the limiting the effect of undesired impurities on the quality of blister copper produced, is also described.

Jan 1, 1998