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By Ker-Chang Hsieh

Four three-phase equilibria and one two-phase equilibrium in the FeNi- S-0 quaternary system in the vicinity of 1023 K and Pso2 = 1 atm were studied using the following emf cell 2 Pt,o2 (air)Zr02 .CaO/Pso2 = 1 atm, mixture of phases, Au The four three-phase equilibria are sp + (Fe,Ni )S + Ni 3s2, sp + Ni 3s2 + NiO, sp + NiO + N1S04 and Fe2 o3 + sp + (Fe,NOS04 -Y:he two-phase equilibrium is sp + (Fe,Ni)S. The two-.phase equilibrium was measured by using mixtures containing a major portion of one phase and a minor portion of the other. The results are presented in terms of oxygen potential as a function of YNi = nNi/(nN1+nFe) at constant temperature and pso2 = 1 atm. The stability diagram was also calculated using appropriate thermodynamic models for all the pertinent phases. The calculated diagram is in accord with the measured ones.

Jan 1, 1985

By Jürgen Antrekowitsch, Thomas Griessacher

The recovery of valuable metals from residues like dusts and sludges is nowadays state of the art. Depending on the complex constitution, a recovery of different metals can – in the majority of cases – only be performed with considerable energy input in high temperature processes together with insufficient yields and newly generated residues. Often, the behavior of the dust or sludge in the process during melting or reduction is unknown. In this work, a detailed characterization of selected residues like steel mill filter dusts, cupola furnace dusts and leaching residues is done. The different steps of getting from solid particles into a homogenous liquid phase were investigated. Although high temperature processing leads to high reaction speeds, the complexity of residues keeps the system away from thermodynamic equilibrium. With this research program, some basics are generated to understand smelting and reduction and the gap between thermodynamical calculations and real behavior can be explained.

Jan 1, 2008

By John Petersen

Heap bioleaching technology has become well established for the exploitation of copper sulfide ores. Still, in many operations the rate of copper extraction is rather slow, often taking two years or more to recover 80% of the copper. Chalcocite, the most common secondary copper sulfide, leaches by a two-stage mechanism. The first stage is rapid, whereas the second stage has a high activation energy and proceeds slowly at ambient temperatures. Nonetheless, this rate is still considerably faster than what is typically realized in a full-scale heap. A comprehensive column bioleaching study of a chalcocite ore has shown that the chalcocite columns are leached in a zone-wise fashion. The first zone corresponds to the first stage of chalcocite leaching, where all ferric produced by the bacteria is immediately consumed and all acid entering with the feed solution is consumed within a relatively narrow band. The second stage of chalcocite leaching proceeds much more slowly in the wake of the first stage, within a zone that grows gradually over the entire length of the column. The overall rate of leaching is thus determined by the rate of acid supply into the column rather than by mineral or bacterial kinetics, at least until the entire column is engaged in second-stage chalcocite leaching. In full scale heaps, there is evidence to suggest that solution distribution favours channelling between relatively large clusters of material which are exposed only to stagnant solution. Reagents have to migrate into such clusters by diffusion, which retards the delivery of acid dramatically. Thus, we believe that the rate of chalcocite oxidation in heaps is governed by sideways diffusion rather than downward migration. Column experimental results have been reproduced with a comprehensive heap-modelling tool. The model predicts that by simply changing the length of the average diffusion channel from column conditions (a few cm) to heap conditions (tens of cm), extraction times can change from weeks to years under otherwise identical conditions.

Jan 1, 2003

By Gunther Schimmel

Ag exudation in four different alloys (Ag-Cd, Ag-Sn, Ag-Sn-In and Ag-Zn) is characterized. The amount of exuded material is correlated with the volume increase due to oxide formation in dependence of the alloy concentration and different densities of the oxide and matrix phases. It is shown that all four alloys show similar amounts of volume increases, but different amounts of exuded material. It is concluded that internal stresses due to the volume increase cannot be the dominant driving force for Ag exudation. A gradient in the chemical potential of Ag that originates from the O concentration gradient inherent to internal oxidation is suggested as driving force. The exudation behavior is thus governed by the variation of the activity of Ag in the Ag fcc phase in the Ag-Me-O system that differs between the alloying systems.

Jan 1, 2010

By Luciano B. Oliveira, Luis G. C. Marques, Sergio N. Monteiro, Marcos V. M. Fagundes

"Biodiesel production is normally associated with large plantations of oily vegetables such as soybean and colza, in large rural areas. However, in the municipal limits of the city of Rio de Janeiro, southeast of Brazil, biodiesel is being produced from wastes commonly generated by typical urban activities such as sewage sludge, discarded fat from meat markets and post-used cooking oils. In the present work, the experience of producing biodiesel from urban wastes in Rio de Janeiro is assessed. The type of precursor materials, equipments and logistics are presented. The environmental and economical advantages as well as the drawbacks are discussed.IntroductionThe interest for a liquid fuel that could substitute those obtained from petroleum started more than one hundred years ago when Rudolph Diesel tested his no-spark internal combustion engine, impelled by compression, with peanut oil. By that time, petroleum was beginning to be extracted in large scale and no one was concerned with the future environmental problems and its eventual depletion. In the last century, the successful association of petroleum based fuels with the automotive industry was an almost insurmountable obstacle to any attempt to use nonmineral oils [1]. In addition to the greater efficiency and, by then, lower price of the diesel from petroleum, the use of plain vegetable oils introduced undesirable carbon deposits and reduced the engine lifetime. Today, the situation is reverse. The continuous increase in the price of petroleum and, above all, its contribution to climate changes are strongly motivating the use of biofuels to replace those obtained from fossil fuels such as petroleum, natural gas and coal [2].In the case of the common petroleum derived diesel, many countries are now engaged in large scale substitution programs. The USA should produce more than 700 million litters of biodiesel, while the European Community is expected too produce around 6.5 billion litters in 2008. In Brazil, the federal biodiesel program imposed a minimum of 2% addition to the common diesel. This would demand a production of 800 million litters in 2008 [3]. The Brazilian biodiesel is made from a diversified source of vegetables mainly castor bean, African palm and soybean. The main producers are agrobusiness firms located in large rural areas of the Brazilian hinterland [4]."

Jan 1, 2008

By Patrick R. Taylor

A kinetic study of the fluosilicic acid leaching of galena was performed under the presence of different oxidants. Fluosilicic acid concentration, agitation speed, concentration of solids and particle size, type and concentration of oxidant, and temperature were the variables studied. Hydrogen peroxide was found to be the most effective oxidant, its effectiveness being proportional to its concentration. As expected, an increase of leaching temperature increased the overall extraction and extraction rate. The same was found by decreasing the galena particle size. It is thought that leaching using hydrogen peroxide is controlled by fluid film mass transfer due to the calculated apparent activation energy. Reaction by-products such as sulfur and sulfur compounds retard the leaching rate. A mathematical model is proposed and compared to experimental results.

Jan 1, 2003

By Wang Yun-yan

In order to examine the adaptability and the kinetics of leaching different gold ores in alkaline thiourea system, six kinds of gold concentrate and/or calcine with different physical and chemical properties were chosen as objects. The leaching behaviors in alkaline thiourea system with high stability, acidic thiourea system and alkaline cyanide system were compared. Changes of phase, surface appearance, particle distribution and specific surface area of six kinds of gold ores before and after leaching were studied in virtue of modern analytic techniques, e.g., XRD, SEM, and so on. The results indicate that alkaline thiourea solution can be used to leach gold ore, for oxidized gold concentrate removed arsenic by microbe pretreatment(4#) the leaching rate of gold is up to 82.68%, such conclusion overthrows the parlance reported that pH value must be less than 1.78, or gold can not dissolve in thiourea solution. Chemical components and phase are related to gold leaching rate, different gold ores are fit for different leaching system, and alkaline thiourea solution is suitable for the pretreated oxidized gold ores with low content of sulfur and in which the main phase was SiO2, phase almost does not change after leaching basically. Generally speaking, when leaching in alkaline thiourea solution, surfaces of gold ores with glaze change greatly to ones with coarseness, distinct trace and holes of corrosion. Particle size decrease and specific surface area increase of gold ores after leaching in alkaline thiourea solution with high stability except gold concentrate of Zhongyuan gold smelter(5#).

Jan 1, 2006

By C. E. M. Meskers, U. Boin

"The increasing use of coated magnesium in consumer products results in creation of coated Mg scrap during product manufacture and after End-of-Life product treatment. Currently this material is generally not recycled, leaving a material resource unused. Closure of the magnesium cycle in a sustainable manner is necessary. In order to do so, the effect of coatings on the recycling process has to be quantified, predicted and minimized. For this purpose metrics have been developed, based on first principles supported by detailed understanding of the recycling process. The developed 3D metric enables quantitative assessment of the recyclability and links coating design, product design and recycling to each other in a visual manner. The parameters that form the metric can be measured and predicted, hence an engineering basis for Design for Sustainability of coated magnesium is provided.IntroductionEvery product progresses through the four phases of the product life cycle depicted by figure 1. In each phase residues are created. Their amount and composition is largely determined by the complex material combinations created/invented during product design in the manufacture phase. Compared to the ideal cycle the magnesium cycle is far from closed (fig. 2). Most noticeable is absence of the link between the EoL phase and raw materials production. A closed cycle only exists for class 1 scrap, which goes from the product manufacture phase directly to production from industrial material and returns to the manufacture phase as magnesium alloys. The four problematic streams are marked by ???. Coated semi-products are present in two of the four residues, namely in rejects and collected scrap. When these semi-products are recycled the amount and composition of the dross and salt slag residue is affected as well.During product design selection of the coating takes place, fixing the coating character¬istics and properties from this moment on for the rest of its life cycle. The choices made in the manufacturing phase are therefore critically linked to the recyclability of coated semi-products as well as the sustainability of the magnesium cycle as a whole. Sustainable closed life cycles, in which the quality of materials is preserved and residue creation and resource depletion are minimized, can be attained by selecting the appropriate alternative during product design. To realize this the effect of design choices on the life cycle and more specific the recycling process has to be known and quantified."

Jan 1, 2008

By G. G. Barbante

Copper anode slimes are a valuable source of the precious metals, and selenium and tellurium. They are mineralogically complex and this has led to a great variety of process flowsheets for treating them. The traditional pyrometallurgical method utilises oxidation in a reverberatory furnace, but has numerous shortcomings. Recently deep-bath intensive smelting methods have been developed for use in the larger refineries. Despite these process advances, the thermodynamics of the reactions involved remains poorly understood. An initial description of the thermodynamics of slimes smelting is presented, but is severely limited by a lack of basic data. It is shown that slimes smelting is superficially similar to copper converting, but has many unique features. More basic thermodynamic data on selenium-based systems are needed before the process model presented can be further refined, and work in this direction has already commenced.

Jan 1, 1994

By Toshiyuki Kozuka

CdTe metal composite semi-conducting material has high potential in good performance of energy conversion efficiency for solar cell and there is much room for improvement of the performance by developing a process of making a thin CdTe film. In this paper, the imposition of intense magnetic field on CdTe electro-depositing surface is proposed, which is one of the possibilities for improving the energy conversion efficiency. In the experiment, cryogen-free super-conducting magnet up to 5T was used and CdTe film was deposited electrically in -o.nv vs. SHE The electrolyte was Cd and Te ammonia alkali solution with controlled temperature in the acrylic cell of 70mm diameter. Electro-deposition behavior of CdTe has affected by the imposition of the intense magnetic field due to microscopic convection in the vicinity of the depositing surface. Electro-deposited surface of CdTe becomes smooth due to microscopic convection around the surface, and the crystallization behavior is also affected, where crystallization temperature and the grain size is changed by the imposition of intense magnetic field.

Jan 1, 2003

By Hélio Wiebeck, Fabio J. Esper, Wildor T. Hennies, Guillermo R. Martín-Cortés, Francisco R. Valenzuela-Díaz

"Natural rubber reinforced commonly with carbon black to produce vulcanized material, turns into a new environmentally friendly nanocomposite when carbon black is replaced by organically modified clays of Brazil. Carbon black is substance derived from the oil refining process with consequent pollution to the environment. Its substitution in this industrial process must contribute to diminish the oil derived products dependence. As the added clays are only a third in weight of the traditionally carbon black added, then, to obtain the same final volume it is necessary to add low cost neutral filler that does not damage the technological characteristics of the final material. This paper presents results using as neutral filler of this type rice husk ashes from industrial wastes. Experiences realized with this nanocomposite material show results of quality and technological characteristics similar or superior to those of the rubber made with carbon black.IntroductionTraditionally rubbers are black or a very dark color. But they can have different appearance when filler of distinct composition of the carbon black is used. The carbon black is substance derived from the oil gotten during the final phases of the mineral fuel treatment with consequent pollution of the environment. Carbon black show nanometric grain sized distribution and a depth black color, because these properties it is also used for computer printers inks production. The substitution of this substance, traditionally used as a reinforced load in the rubber production, will have to contribute in such a way to diminish the dependence of these products as to diminish the pollution of the environment. The present work shows the results of the use of another kind of mineral nanoparticulate material substituting carbon black in the production of some rubber products. This nanoparticulate material is the organic modification of smectite clay treated with some types of ammonium quaternary."

Jan 1, 2008

By Erik Olsson, Gunilla Hyllander, Stefan Schuster, Lena Sundqvist Ökvist, Maria Lundgren, Michael Hensmann, Olavi Antila

"Residual materials from the integrated steel plant itself or other sources often contain valuable compounds of e.g. C and Fe. Dust and sludge have to be agglomerated to be able to recycle to the blast furnace (BF) via top-charging. By injection of the materials, preparation methods in terms of e.g. drying and/or screening only, can be used. Alternative carbon materials (ACM) in terms of BF dust and sludge have been successfully injected up to levels of 60 kg/tHM in the LK.AB Experimental Blast Furnace (LKAB EBF®). Efficiency in recovery of valuable compounds as well as the behavior of undesired elements have been evaluated and are discussed.IntroductionTraditionally, recycling of steel in-plant fines is made via the sinter plant and blast furnace route. Steel plants operating with 100% pellet as ferrous burden and have no sinter plant. There are limited areas for land fill and costs are caused for preparation of landfills and deposit fees. Very fine paniculate dusts or sludges cause decreased productivity and increased coke rate in the sinter plant, and therefore other ways for recycling must be considered. Injecting them into the BF could be an economically and technically feasible alternative. Additionally, as the materials contain valuable compounds of e.g. C and Fe."

Jan 1, 2012

By Jr. Robison

"Aluminothermic (""thermite"") smelting became commercial with the development of tonnage aluminum, and prospered producing metals and alloys with higher cleanliness, consistency and elemental control than competing technologies. We explore the scope of thermite smelting, and metallothermic smelting in general; the thermochemistry of the process; and its advantages and limitations as applied to industrial production. We review currently-produced products of thermite smelting in several forms and a wide range of heat sizes. As these products serve several industries, we relate the demands of those industries to the requirements imposed on the thermite process, leading to process dynamics and mechanisms to control/alter those dynamics. We review ways to lower the process costs by altering process stoichiometry, using other energy sources and utilizing less costly materials while considering effects on product quality and customer requirements. Finally, we examine overall emissions control and waste disposal.IntroductionAluminothermic smelting is the reduction of various oxides by aluminum to produce metals or alloys with varying levels of residual aluminum. One of the earliest uses of the process was the production of liquid iron to weld railroad rails, later modified in ""thermite grenades"" used to ""spike"" artillery pieces in World War II. Then during the 50's, 60's and 70's the growth of jet aircraft created a demand for new superalloys and titanium alloys, both requiring master alloys for efficient production. Aluminothermic smelting grew with the aerospace industry and with the expansion of microalloyed steels. It is very much a niche industry, dependent on the specialized demands of the specialty steel, superalloy and titanium industries. In this paper we introduce the characteristics of aluminothermic smelting, the scope of smelting operations, the markets served, and the environmental aspects of the process, as seen through the eyes of a company using aluminothermic smelting for over fifty years"

Jan 1, 2012

By Chris P. Pistorius

Over the past few decades the carbon intensity of ironmaking and steelmaking has been reduced considerably through improved efficiency in blast furnace ironmaking, partial replacement of coke with less carbon-intensive fuels, and increased use of scrap and direct-reduced iron in steelmaking. To evaluate possible further reductions in carbon intensity accurate process information is needed. A preliminary test of the fidelity of publicly reported data as a source of process information is reported here. The sources are industry roundups of electric furnace furnace steelmaking and blast furnace ironmaking (published by the Association for Iron and Steelmaking Technology), and data recorded by the Environmental Protection Agency under the US Greenhouse Gas Reporting Program. From a comparison for an integrated steelmaking plant and an electric furnace furnace plant, it appears that the values from the two data sources are consistent. The comparison does rely on process details such as the quantitative relationship between injected oxygen and carbon emissions in electric furnace steelmaking.

By N. B. Gray, I. F. Taylor

"Gas injection to promote chemical reactions or mixing is a feature of many metallurgical processes. Often the aim of gas injection is to bring about a chemical reaction between the gas and liquid but most of the past physical and mathematical modelling work has ignored the influence of such reactions. In the work reported here, cold model studies have been conducted in which gas reacts with the liquid into which it was injected. The rate of liquid mixing has been measured as an indication of the mechanical energy transfer. It has been found that gas generated chemically within the liquid is significantly less effective at promoting mixing than the equivalent volume of inert gas. The relative ineffectiveness of chemically produced gas is thought to be due to smaller bubble sizes in comparison to the inert gas case. Small bubbles characteristic of chemically generated gas move with low slip velocities relative to the liquid and lead to different turbulence generation mechanisms.IntroductionIn processes such as steelmaking, copper conversion, bath smelting and ladle steel finishing gas is injected into liquid metal where it reacts chemically or simply serves as a source of agitation. An understanding of fluid flow phenomena in such situations is an essential pre-requisite to the calculation of process intensity and the optimisation of vessel productivity. Traditional physical cold modelling approaches to prediction of liquid flow in such situations are now often augmented by the techniques of computational fluid dynamics. Even with the availability of numerical modelling techniques cold physical models continue to have an important role for validation because it is generally difficult to obtain quantitative data from high temperature processes.Almost all previous cold modelling work has been based on the injection of an inert gas into water or some other non-reactive liquid. Such models do not include the significant increase in gas volume inherent in some processes. For example the oxidation of carbon in steelmaking leads to a twofold increase in molar gas flux through the reaction:"

Jan 1, 1996

By E. C. T. Chao

Micro-optical and synchrotron radiation-induced X-ray fluorescence (SXRF) techniques have been used to study unoxidized and oxidized samples of Carlintype sedimentar,y rock-hosted disseminated gold ore. In these samples, Where much of the gold is submicroscopic, the SXRF technique, which has a spatial resolution of about 20 ~m and a minimum detection limit (MDL) in the ppm range, is an ideal and necessary tool for precisely locating gold-rich areas in a sample. Gold-rich areas pinpointed by SXRF were later studied in detail by micro-optical methods, principally optical microscopy and scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDX). In two unoxidized and one oxidized ore samples, SXRF analyses have shown gold to be present predominantly in discrete clay-rich and silicified areas. Gold was not detected by SXRF in association with pyrite or carbonaceous materials. SEM-EDX examination of the gold-bearing areas in the unoxidized samples succeeded in identifying only two free gold particles, 0.2 and 0.5 ~m in size. In the oxidized sample, gold particles appear to be larger (but still submicroscopic) in average size and more evident in micro-optical examination after SXRF location of goldbearing areas. The findings of these studies may help to improve the efficiency of processing and recovery of gold from unoxidized ores.

Jan 1, 1987

By T. L. Baum

External oxidation during in-line heat treatment of TRIP steels can cause problems for the subsequent coating process. This research aims to elucidate the kinetic rates of internal oxidation, external oxidation and decarburization and their interdependence under different gas atmospheres and temperatures. A rolled steel sample chemistry of 0.14 wt.% C, 1.8 wt% Mn, 0.6 wt.% Si and 1 wt.% Al is used as a case study. Thermogravimetric techniques are used to examine the net mass change in a sample during heat treatment and the results show an initial mass decrease and later an increase for particular partial pressures of H2O. SEM-EDS, optical microscopy and glancing-angle x-ray are used to quantify the microstructure. The cross-section of the samples have 4 distinct zones: (i) an external scale, rich in fayalite, (ii) an internally oxidized region with Al, Si and Mn oxides in an Fe matrix, (iii) a decarburized steel region, characterized by large ferrite grains and low carbon content, and (iv) a relatively unaffected steel core with a structure similar to the starting material.

Jan 1, 2006

By Arthur G. Hunt

Smelting using the direct-to-blister process commenced at Olympic Dam on 31 July 1988. The unique nature of the Olympic Dam ore body led to the selection of the direct to blister smelting process. Significant improvement in the design of the furnace and the understanding of the fundamentals of the process and its operation has occurred in the 10 years of operation. The paper will discuss the operation of the #1 Smelter and the design, preparation for start up and early operating experience of the #2 Smelter.

Jan 1, 1999

By Funsho K. Ojebuoboh

With several "green" applications in the horizon, bismuth has become an even more important minor metal in the smelting and refining of lead. Smelters with a complex sulfide feed invariably deal with bismuth. Its behavior during the smelting of lead in conventional sinter - blast furnace operation is discussed. Because it readily deports to the lead phase during the refining of lead, its separation from refined lead remained unsatisfactory in early lead production. When commercial requirements of bismuth in lead became more stringent early this century, the procedure whereby calcium and magnesium is used to debismuthise lead was developed. The present conduct of this 1936 process, the Kroll Betterton process, is discussed with emphasis on operational improvements.

Jan 1, 1995

By Jinxing Ji

Several fundamental aspects related to the nickel electrowinning from chloride electrolytes have been addressed in this paper. The thermodynamic study includes the activity coefficient of the hydrogen ion and the speciation diagram of NiCI2 solutions. The activity coefficient of the hydrogen ion (YH+) was calculated and estimated experimentally using a combination glass pH electrode. It was found that YH+ was greater than one in concentrated NiCl2 solutions and increased significantly with increasing NiCl2 concentration. The speciation diagram for NiCl2 solutions was plotted with YH+ and the effect of the ionic strength on the equilibrium constants being taken into account. It was discovered that the predominant nickel species in the acidic region were Ni2+ and NiCI+ in 0.937 M NiCl2 solution at 25°C. Electrodeposition tests demonstrated that higher Nit' concentration in the electrolyte improved the current efficiency of nickel electrodeposition (CENi). The additions of H3BO3, and NH4Cl increased very little the current efficiency of nickel electrodeposition at pH 1.5 and temperature 60°C. However, the addition of sulfate decreased the current efficiency of nickel electrodeposition. Nickel electrodeposition was also found to be a steady-state process since the amount of acid added to the electrolyte at a constant pH increased linearly with time during galvanostatic electrodeposition. The cathode surface pH during nickel electrodeposition was measured using a flat-bottom combination glass pH electrode and a 500-mesh gold gauze as cathode. The cathode surface pH was found always to be higher than the pH in the bulk electrolyte, and if the current density was sufficiently large, it would eventually reach a level causing precipitation of insoluble Ni(OH)2(s) on the cathode surface. Rotating disc electrode studies revealed that the rate of nickel electrodeposition was first order with respect to the activity of nickel ion and zero order with respect to the activities of chloride and hydrogen ions. The rate of hydrogen evolution was found to be first order with respect to the activity of hydrogen ion and to be zero order with respect to the activities of nickel and chloride ions. These findings indicate that nickel deposition and hydrogen evolution proceed independently.

Jan 1, 1995