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By Andreas Siegmund

Cast or rolled lead anodes employed in zinc electrowinning typically contain between 0.5?1.0% silver to decrease the overall corrosion rate. The production of cast lead-silver or lead-silver-calcium anodes often results in the formation of numerous holes, voids or laps in the anode surface that can initiate internal corrosion in localized areas. In rolled anodes the presence of internal porosity is significantly reduced, thus resulting in extended service life. The obtained grain structure of cast or rolled Pb-Ag anodes, however, requires a relatively long period of time to form a stable protective PbO2/MnO2 layer that can evolve oxygen without excessive lead contamination of the cathode. Therefore, these anodes are often mechanically, chemically or electrochemically conditioned prior to being placed in the electrowinning process. RSR Technologies has developed an improved anode for zinc electrowinning. The anode consists of a rolled Pb-Ag-Ca-alloy with controlled surface grain structure. The preferred calcium and silver content of the alloy is 0.05?0.08 % and 0.3?0.4%, respectively. Since May 2001, industrial-scale tests have been carried out at two zinc refineries in North America in industrial electrowinning cells. The controlled grain structure of these anodes allows forming an adherent protective oxide coating within a short period of several days when placed in an electrowinning cell without the necessity of being preconditioned. Anode sludge growth is evenly distributed. The anodes stay dimensionally stable and no short-circuits have been observed. Consequently, low corrosion rates and improved current efficiencies have been achieved.

Jan 1, 2003

By Mohamad Omarei, S. M. Sadrameli

"The aim of this research work was to produce biodiesel (fatty acid methyl esters, FAME) from canola oil using KOH loaded on y-Al203 support as a heterogeneous catalyst. Different parameters such as effects of the molar ratio of methanol to oil, catalyst amount and reaction time on the yield were investigated. Scanning electron microscope (SEM) and X-ray diffraction (XRD) were used for characterization of the catalysts. A biodiesel yield of 86.67% was obtained under catalyst preparation and transesterification conditions of calcinations temperature of 773 K, 4 h of reaction time at 338 K, and using 3.5 wt% catalysts and molar ratio of methanol/oil of 15:1. The leaching of potassium species in the spent catalyst was observed.1. IntroductionBiodiesel is an eco-friendly and alternative energy source for diesel engines that can be synthesized by transesterfication of vegetable oil or animal fat with alcohols [1 ]. There are four principal approaches to the synthesis of biodiesel involving the transesterification of the triglycerides of the plant oils and animal fats: base catalysis [2], acid catalysis [3-5], employing supercritical alcohol conditions [6] and enzyme catalysis [7]. The commonly used homogeneous catalysts are NaOH, KOH and their alkoxides. Homogeneous alkali-catalyzed transesterification is much faster than acidcatalyzed transesterfication [8]. However, a large amount of water is required to transfer the catalysts from the organic phase to a water phase after the reaction. Therefore, it is considerably more costly to separate the catalyst from the produced solution [9]. These disadvantages could be removed by use of a heterogeneous catalyst [10]. The use of heterogeneous catalysts eliminates the neutralization step, hence it results much easier to separate from liquid products. Also, they can be designed to give a higher activity and selectivity and to have longer catalyst lifetimes [11]. A large number of different heterogeneous catalysts have been synthesized for biodiesel production. For example, calcined Mg-Al hydrotalcites [12], zeolite and metal catalysts [13], metal oxides such as calcium oxide (CaO) [14], magnesium oxide (MgO) [15], zirconium oxide (Zr02) [16], and supported catalysts [17] have been investigated as heterogeneous catalysts. CaO and MgO are most frequently used heterogeneous catalysts for biodiesel production [18]. In this present work, we aimed at developing an efficient catalyst for transesterification of canola oil. We have prepared KOH/ Al203 by impregnation and applied to determine the optimum conditions for biodiesel production. Three different variables including reaction time , alcohol to oil molar ratio and catalyst loading with may influence the quality of the produced biodiesel were optimized. Moreover, SEM (scan electron microscope), XRD (X-ray diffraction) and XRF were used for characterization of the catalysts."

Jan 1, 2012

By G. T. Lapidus, O. J. Solis-Marcial

"The oxidative dissolution of copper from refractory minerals, such as chalcopynte, represents a technological challenge that has occupied hydrometallurgists for more than half a century. Innumerable processes have been suggested, but the majority operates at high temperatures or employs corrosive media. The origin of this refractory nature is the formation of passivating phases of iron(III) or copper. One option is to add non-corrosive ligands that complex these metal ions, thereby facilitating their dissolution. In the present work, the effect of acetone in sulfuric acid solutions was studied. The initial experiments were on chalcopynte carbon paste electrodes using cyclic voltammetry, where greater reactivity was observed. Later, leaching tests with hydrogen peroxide, cupric sulfate and ozone and, as oxidants, were performed. High extractions were achieved in three hours at 50°C. The solid residues contained the iron in the form of Fe203 and FeOOH.IntroductionChalcopyrite is the most important mineral of polysulfide copper ores [1] and accounts for approximately 70% of the world's copper reserves [2]. Currently, the copper present in chalcopyrite is extracted mainly by pyrometallurgical processes, which generate environmental concerns because of the formation of SO2 gas and submicron particulates [3]. The development of a less aggressive hydrometallurgical process for the extraction of copper would constitute a possible solution to these problems. For that reason, studies of the dissolution behavior of chalcopyrite are of great technological importance [4], However, the proposed oxidative leaching routes for chalcopyrite, generally at high pressures and temperatures, have not been implemented on an industrial scale, because of the elevated costs required to equal the high copper extractions obtained in thermal processes. These extreme leaching conditions are required because of the refractory nature of chalcopyrite. Passivation has been used to explain this phenomenon, although researchers have disagreed on the composition of the layer, which is various have assumed to be sulfur, copper sulfides, and iron-bearing jarosites or hydroxides [5]. If the latter compounds are the cause, an alternative solution would be the use of polar organic solvents in the oxidative leach to decrease the formation of the passivating iron layer. In this work, the influence of acetone on the oxidative leaching of a chalcopyrite concentrate at room conditions is explored."

Jan 1, 2012

By Xiaodi Huang, Matthew Andriese, Zheng Zhang, Jiann-Yang Hwang, Zhiwei Peng

"The thermal decomposition and regeneration behaviors of wüstite were investigated by in situ high temperature X-ray diffraction (HT-XRD) under non-isothermal condition at heating rate of 4 K min-1 in vacuum ranging from 294 K to 973 K. Wüstite on heating decomposes to magnetite and iron up to 823 K, above which it exhibits marked tendency to regenerate. Investigation of thermal stability of the reaction system shows that the decomposition proceeds under kinetic reaction control while the regeneration is under thermodynamic control. Kinetics study based on the Coats-Redfern integral approximation method indicates that the decomposition reaction follows a Komatsu-Uemura model-based diffusion-controlled kinetics with activation energy of 32.860 kJ mol-1. The thermodynamics analysis of regeneration reaction demonstrates that wüstite regenerates at lower temperature than stoichiometric ferrous oxide.IntroductionOwing to its importance in preparing various magnetic ceramic/metal nanocompostites or nanocrystals with high values of coercivity for the application as recording media, wüstite (non-stoichiometric ferrous oxide) has been attracting the attention of scientists over a long period [1-6]. The thermal behavior of wüstite was investigated by several researchers and phase transformations due to thermal decomposition and regeneration of wüstite during the heating in a specific temperature range was observed [7-9]. In spite of wüstite being found to dissociate to magnetite and iron at temperatures lower than 848 K and then regenerates at higher temperature, a clear understanding of the reaction mechanisms is clearly lacking [9]."

Jan 1, 2012

Accretions of dust on the walls of the offtakes from furnaces and in the waste heat boiler are a cause of significant operating and maintenance problems in non-ferrous smelters. The dust originates from entrained solids in the gas stream and vaporised species that condense during gas cooling. Control of dust formation is very important for minimising the formation of accretions and reducing the severity of environmental problems caused by toxic species, such as those containing arsenic, in the dust. The present paper discusses the formation of accretions and the condensation of dust in copper smelting from a thermodynamic viewpoint. Changes, in gas composition and the amounts and identities of the condensed species in the dust are calculated using computational thermodynamics. Interactions between dust species to form accretions are considered in the light of appropriate phase equilibria. The results show that the nature of the dust formed varies greatly, depending on the temperature and the amount of oxygen present during cooling. Control of the amount of oxygen is required if offtake and waste heat boiler accretion problems are to be minimised.

Jan 1, 2002

By Rodney T. Jones

DC arc furnaces were first used industrially for the reductive smelting of chromite fines to produce ferrochromium thirty years ago. Since then, they have been used for a variety of applications, including the smelting of ilmenite to produce titania slag and pig iron, the recovery of cobalt from non-ferrous smelter slags, and the smelting of nickel laterite ores to produce ferronickel. The power of these furnaces has increased from 12 MW to 72 MW for ferrochromium, and to 80 MW for ferronickel. The largest of these furnaces requires two electrodes to carry sufficient current to generate this much power. A review is presented of various DC arc furnaces in use, along with a discussion of the likely ways in which furnace power might be increased further in the future.

Jan 1, 2014

By Ryosuke O. Suzuki

A combined process of electrolysis of CaO in the molten CaCl2 and of calciothermic reduction, so-called OS process, was applied to prepare metallic vanadium directly from V2O3. The fine metallic powder containing 1860 mass ppm oxygen was obtained using 0.5mol%CaO-CaCl2 melt for 10.8 ks at 1173 K. The oxygen level did not decrease further even when twice electricity was applied. Because the metallic vanadium could be electrochemically deoxidized to the level of 10 ppm oxygen from 1.48 %, the large amount of by-product, CaO, due to reduction and the large surface area of the fine particles are the reasons of high oxygen content in the reduced powder.

Jan 1, 2006

By Forsén. O.

In this ?paper practical solidification of anodes containing nickel, arsenic, antimony and bismuth is compared with the equilibrium? diagrams and kinetic ?factors. In order to clarify the distribution of the impurity elements in the anode the structures were studied after the solidification and also after the electrolysis of anodes. This examination was carried out with optical microscope, scanning electron microscope and electrochemical measurements. All the nickel is remaining metallic in the copper matrix during the solidification and therefore nickel is dissolved in the electrolysis at all oxygen contents, when the nickel content is 0.25 wt-% or less in the anode. The practical .solidification mechanism of the anodes, when the nickel content exceeds 0.25 wt-%, proceeds by the crystallization of nickel oxides. In oxygen containing copper anodes nickel oxide is verified to crystallize together with antimony in certain conditions and to form a micaceous compound (3Cu2O?4NiO?Sb2O5), which may build up a very harmful floating slime in the electrolyte. Arsenic is strongly enriched along the phase boundaries in oxygen free copper anodes. An intermetallic compound Cu3As is formed when the amount of arsenic in the anode. exceeds 0.7 wt-%. This compound is more noble than the copper matrix. This means 'that a selective dissolution of copper-arsenic compounds takes place. The copper matrix dissolves more strongly than the grain boundaries. The solidification structures of oxygen free bismuth containing copper anodes show clearly the influence of bismuth. Thin bismuth films which are less .noble than the metallic copper matrix, are formed during the solid1ficatton process. As a result of this the?grain boundaries are dissolved faster than the copper matrix.

Jan 1, 1987

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 Günter Petzow, Hans Leo Lukas, Hans Jürgen Seifert

"The CALPHAD method (CALculation of PHAse Diagrams) has been extensively developed in the last 25 years and became a useful tool in materials science. Thermodynamic descriptions for the functions of state of unary, binary and ternary phases are derived by the optimization of phase diagrams. These functions are stored in computerized thermochemical databases and can be combined to extrapolate to multi component systems. Depending on special demand, the actually most advantagous presentations of the calculated results can be chosen: tables or in a clear graphical form as phase diagrams, phase amount diagrams or volatility diagrams. The method will be desribed by the system Ti-Si-C-N-O including the ceramic subsystem Si3N4-SiC-TiCi,N1_1,-C-N-O which is very important for the development of ceramic composites. The calculations give the thermodynamic stabilities of the condensed phases as function of temperature, concentration and partial pressure of different gas species. Adjusting the sintering conditions to these results the formation of unfavourable compounds or liquid phases can be suppressed.IntroductionThe CALculation of PHAse Diagrams (CALPHAD-method) of multicomponent systems provides the possibility to plan experiments very efficiently and avoid the experimental trial and error approach for the development of materials. The main problem for best use of calculated results is their interpretation with regard to the specific applications under consideration. Tables give the exact quantitative data for the treated phenomena. However, most important to make best use of these thermodynamic data is their graphical representation especially designed for the solution of specific problems, scientific as well as application oriented. Only well chosen graphical representations support a comprehensive understanding of the thermodynamic interrelationships and the transfer to the problem."

Jan 1, 1996

By M. H. Staia

A Venezuelan ilmenite concentrate has been chlorinated at a temperature of 700" C by carbon tetrachloride. In the experimental rig, built at laboratory level, the direct chlorination process yielded a TiCI, recovery of approximately 85% after 280 minutes processing. The partial pressure of carbon tetrachloride was nearly atmospheric (0.94 atm). Product vapors from the reactor were fractionally condensed in a condenser which was maintained at a temperature of 250°C meanwhile TiCl, vapors were condensed in refrigerated coils at a temperature of -20°C. The concentrate used in this investigation was obtained by applying gravitational and magnetic concentration methods to the black sands. The experimental results have shown the need to asses the influence of the weight ratio of ilmenite to carbon tetrachloride on the resultant products. The equilibrium of the heterogeneous system has been calculated taking into account the initial experimental conditions.

Jan 1, 1995

By S-L. Jämsä-Jounela

Fault diagnosis systems have attracted growing interest in a number of engineering fields. The number of applications has increased and successful results have been widely reported. The fault diagnosis system presented in this paper is integrated, and it monitors the states of the process and performs fault detection and diagnosis on the process equipment. The monitoring of process states is carried out by means of Kohonen Self-Organising Maps that is a powerful tool in visualisation and analysis of high dimensional data in engineering applications. This paper presents the results of SOM analysis carried out on the Outokumpu flash smelting process. The subsystems analyzed in more detail are the condition of the concentrate burner, the condition of the gas line on the basis of the pressure distribution in the process and the cooling water circulation of the waste heat boiler, and the condition of the furnace and furnace equipment on the basis of the temperature distribution in the furnace and gas line. Keywords: Fault diagnosis, Process monitoring, Kohonen Self-Organising Maps, flash smelting

Jan 1, 2001

By R. L. Miller

An industrial wastewater, including plating wastes, is treated with sodium sulfide and ferrous sulfate to form a sulfide-oxide precipitate containing chromium and other toxic metals. Hydrocarbons, in the water, coat the sulfide-oxide particles, impeding metal recovery. Froth flotation, without reagent addition, was found to recover 93.9% of the solids from the sludge with simultaneous rejection of 89% of the water. Methyl isobutyl carbinol (MIBC) improved recovery and potassium amyl xanthate improved both recovery and grade. The process design has wastewater feed (without MIBC) to the rougher circuit. The rougher concentrate is conditioned with MIBC and fed to a cleaner circuit to achieve a high grade concentrate. About 95% of the water is recirculated to the waste treatment plant.

Jan 1, 1992

By P. E. Donaldson

Since 1992, Falconbridge has made available to the international copper industry, Kidd Creek's licensed refinery process technology under the name of the Kidd Process. This has resulted in the supply and installation of permanent cathodes and associated product handling equipment to refineries in Canada, the United States, South Korea, Chile and Mexico. These installations accommodate both electrorefining and electrowinning processes. The growth and industrial acceptance of the Kidd Process has generated technical advancements in the areas of product random sampling, corrugation, marking, labeling, product tracking and data acquisition. In a different area, the expanded development of custom materials processing at Kidd created a need to advance technologically. The process-related problem of high nickel concentrations in refinery electrolyte compromised an increase in current density to >300 A/m2. The need for nickel removal resulted in Kidd Creek's newly developed Nickel Recovery System. The effective and economical extraction of nickel, along with reduced antimony and bismuth levels, reduces bleed stream volumes and/or neutralization costs and simultaneously produces a marketable nickel carbonate product.

Jan 1, 1999

By G. G. Krishna Murthy

Several experiments were conducted to determine the rates of heat transfer coefficients of CaO-SiO2-A1203-FeO slags at temperatures in the range 1623-1823 K The experimental technique involved measuring heating rates of a solid specimen, sub¬merged in slag phase, using a temperature probe made of Pt\ 10%Rh-Pt. Effect of %FeO (3-10%), %FeS (0.1-0.68%), %P205 (0.2-3.0%), %MgO(5-6%), and %MnO (0.96-3.84%) present in the slag on overall heat transfer coefficient, U, of slags was investigated. Simple first order heat balance equation in combination with experimental plots rising temperature of solid specimen versus time were employed to determine the values of U. The values of U determined in the present investigation were present in the range of 70-260 cal/Ks.m2. The value of U increased with increasing the slag temperature. The values of U were not effected by increased amounts of sulfur in the slag phase. The increased concentrations of MgO, FeO, MnO, and P205 in the slag phase decreased the values of U. On the other hand, the increased amounts of Fe2O3 in the slag phase increased the value of U. Comparison of the results, obtained using the slag bath stirred by argon injection, with those determined without any stirring indicated that both radiative and conductive heat transfer mechanisms are important even at high temperatures.

Jan 1, 1993

By Toshio Suzuki, Machiko Ode, Won Tae Kim, Seong Gyoon Kim

"The Ostwald ripening and growth and coarsening of the secondary dendrite arm are studied using a phase-field model. The phase-field parameters are obtained at a thin interface limit proposed by Kim et al. In Ostwald ripening analysis, the difference of the concentration due ·to· the curvature effect is shown. The third power of the average particle radius Rav is proportional to time and the ripening constant shows a good agreement with the value by Deppers et al. The particle radii distribution shows the transition behavior to attain a self-similar stationary shape. The growth and coarsening behavior of the secondary dendrite arm is also analyzed using a phase-field model. The estimated arm spacing and its dependence on time are in good agreements with experimental data.IntroductionThe ripening or coarsening process controls the microstructure during the late stage of solidification. The ripening phenomena are recognized firstly by the Ostwald [1]. The first quantitative analysis for the Ostwald ripening in the limit of vanishing solid fraction was provided by Lifshitz, Slyozov and Wagner (LSW) [2,3]. In their study, that the mean radius grows proportional to the cubic root of time and the size distribution of precipitations shows a ""self-similar"" shape are shown. Most of the studies for the Ostwald ripening confirm or predict these two general rules above. In case of finite solid fraction, the general rules are observed but the ripening constant is larger and the self-similar shape is wider than the LSW prediction respectively [4-6]. To analyze· the high solid fraction system, the theories that consider the solute field correlation are proposed [4,7-8]. In the theory, however, since the particle is treated as the point, the effect of the concentration field deviation from the monopole field should be taken into account. Recently the numerical simulation, in which not only diffusive transportation of solute but also convection effect is considered, has been done using a phase-field model [9]."

Jan 1, 2000

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 K. S. Kawatra

In recent years, there have been several efforts to develop binder mixtures for iron ore pelletization. Some efforts have been fruitful, while others have encountered failure. For example, adding corn starch to bentonite is effective, while adding fly ash to bentonite is not. When binders are made with fly ash, a pozzolanic reaction occurs, but no such reaction occurs when bentonite and corn starch are used together. The authors analyzed which binders can be mixed, and which binders will succeed. The authors confirmed this analysis with several laboratory and plant studies. This paper presents this critical analysis, along with various combinations of binders for making Iron Ore Pellets.

By Scott A. Howard

MgO is routinely used as the basis for refractory materials, however, its susceptibility to hydration may result in dimensional instability and subsequent failure. The addition of boron has been shown to reduce th,e hydration susceptibility of MgO yet its dissolution into certain grades of steel may degrade their performance. In order to predict the efficacy of reducing hydration susceptibility by the incorporation of mono-, di-and tri-and quadravalent cations, the lattices of various cation-substituted systems were modeled. To more accurately simulate the substituted lattices, either cation or anion vacancies were incorporated to maintain electrical neutrality and all possible arrangements of defects in a 2x2x2 MgO supercell were investigated. Correlations were then made between the lattice energies of these systems and their susceptibility to hydration as reported in the literature. The results indicate the presence of higher charged cations tended to increase lattice stability while the cations with lower valency tended to have lower lattice energies. The relatively small body of experimental results available in the literature are consistent' with this study's results.

Jan 1, 1989

By Margarete Kalin

Mine abandonment is associated with the securing of access to underground workings, shafts, raises and adits. Waste rock piles and tailings are generally contoured and revegetated. When the waste materials contain pyritic material seepages can often emerge long after the physical reclamation work has been carried out. Their extent and origin has to be delineated to facilitate remedial measures. The depth to which the seepages extended can be determined with an electromagnetic (EM) survey. This paper reports on the experience gained using a winter and a summer EM survey correlated with measurements of specific conductivity at the sediment water interface. Lake sediments and ponds which represent a homogenous background material are good media, where specific conductivity and electromagnetic conductivity can be correlated. The origin of the seepage within the recontoured mine site requires detailed site knowledge, as many anomalies in heterogenous materials such as represented by a mine site are evident.

Jan 1, 1994