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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 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 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

The present work is mainly focused on developing intermetallic inert anodes for aluminum electrolysis. The anode alloy based on Al-Ti-Cu system was prepared by casting, followed by the application of a protective coating. Behaviour of corrosion and the passivation under anodic condition was characterized using the electrochemical and microscopic techniques. The results obtained clearly demonstrate that the oxide coating can provide good corrosion resistance via surface passivation of alloy anodes, rendering them inert in cryolite melt.

Jan 1, 2006

By T. T. Chen

Kidd Creek continuously-cast copper anodes are characterized by high levels of Se, Pb and Ag; the anode slimes constituents and their morphologies are controlled by both the anode composition and the casting process. Hollow Cu2Se spheroids and tube-like structures, enveloping Cu-Pb-As oxide and/or Cu2O, are present in the as-cast copper. During electrolysis, the selenides are liberated from the copper and accumulate in the slimes layer; the Cu2O and Cu-Pb-As oxide react rapidly with the electrolyte to form soluble species and PbSO4. Silver, which is present mostly as a solid solution in the anode copper, is also liberated during electrolysis and reacts with the Cu2Se to form (Cu,Ag)2Se. The ultimate composition of the selenides in the slimes layer depends mostly on the Ag and Se contents, but various other elements, including Au and Te, are also structurally incorporated. Although the selenides are the major Ag carrier, metallic silver also is present. A thin layer of Cu2O crystals sometimes forms at the copper surface, and may affect anode passivation. Copper sulphate is a common constituent and serves to agglomerate the slimes. Copper sulphate is present on both passivated and non-passivated anodes, but that observed on the passivated metal is present as a thick compact layer. Copper powder is associated with CuSO4.5H2O only on passivated surfaces.

Jan 1, 1987

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

By S. J. Macnaughton

The Olympic Dam deposit in South Australia contains 2% copper and 0.06% uranium, which are present as bomite, chalcocite, chalcopyrite, uraninite, coffinite and brannerite. The copper is principally recovered using flotation. The flotation tailings, which contain the bulk of the uranium, and typically 0.3% copper, are leached using sulfuric acid and an oxidant at atmospheric pressure. This paper describes the results from a detailed investigation of the leaching behaviour of this ore. The influence of acid strength, Fe3+ concentration, redox potential and temperature on the dissolution of uranium and copper minerals was studied. Experimental data were obtained from extensive batch leach tests. Mineralogical studies, including SEM analysis of individual mineral grains, were also carried out. The maximum extraction of uranium determined experimentally was in good agreement with that predicted from SEM determination of the proportion of refractory brannerite in the ore. The leaching rate of copper was found to be independent of acidity over the range 20 g L-' to pH 2.0, but was strongly dependent on temperature and Fe3+ concentration. Uranium extraction showed a weak de endence on acidity, Arrhenius temperature dependence and a complex co-dependence on F>+ concentration and redox potential. A kinetic model has been developed, which predicts copper and uranium dissolution. This model will be incorporated into a more comprehensive model that can be used to predict leach performance and reagent consumption for specific ore samples.

Jan 1, 1999

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

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 N. Krishna

The utilization of Electrochemical Impedance Spectroscopy (EIS) in conjunction with Atomic Force Microscopy (AFM) is a powerful surface characterization technique to study the role of sulfur formation during acidic oxidation of chalcopyrite. It has been established that the chalcopyrite dissolution kinetics is controlled by the formation of passive sulfur layer during leaching. The objective of the study was to characterize the intermediate sulfur layer formation at different oxidation conditions in acidic solution. The chalcopyrite samples were subjected to anodic oxidation and the oxidation process was analyzed using impedance spectroscopy. The sulfur growth on the chalcopyrite surface during oxidation was further analyzed using Atomic Force Microscope for sulfur roughness and grain size, peak height and sulfur growth.

Jan 1, 1999

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 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 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 A. G. Cecutti

A brief overview of the known significant health effects of both Nickel and Cobalt will be presented. Some time will be given to the current research activities, especially for Nickel. Emphasis will be placed on some of the controversial issues associated with their health effects.

Jan 1, 1988

By J. A. Gonzalez-Dominguez

During the electrorefining of lead by the Betts process, ionic concentration gradients become established within the slimes layer. These gradients contribute to precipitation of secondary products and to gradients in electrode potential applied to slimes filaments, and thereby affect the dissolution of noble impurities. This paper describes the experimental results obtained when a typical lead anode was dissolved under galvanostatic conditions with concurrent interruption of current at preset slimes thicknesses. Reference electrodes were incorporated within the lead anode to follow the potential gradients across the slimes electrolyte. Samples of the slimes electrolyte were withdrawn in-situ and their compositional changes were related to transport processes across the slimes layer. Upon current interruption the anodic overpotential decays, first abruptly (as the uncompensated ohmic drop disappears), and then slowly (due to the presence of a back E.M.F. created by ionic concentration gradients that decay slowly). Current interruption measurements showed that: (A) concentration gradients exist across the slimes layer, (B) inner solution potentials within the slimes layer can be larger than those measured from reference electrodes located in the bulk electrolyte, (C) secondary products can shift the inner solution potential to negative values that reverse upon re-dissolution and (D) ionic diffusion is seen upon current interruption but it is complex and difficult to model due to the presence of processes that can support the passage of internal currents. SEM and X-ray diffraction analysis of the slimes filaments indicated that secondary reactions leading to the formation of Si02 and PbF2 take place (mainly at the anodelslimes interface). The onset of these reactions and their relationship to the Pb-F-Si-H20 Eh-pH diagram are linked to the industrial operation of the Betts process.

Jan 1, 1994

By Philippe Henry

"Hydrometal provides an adequate technology to reintroduce otherwise lost metal units into the industrial cycle, thereby saving resources and energy, while keeping the environment cleaner. Two case studies at an integrated hydrometallurgical recycling facility (Hydrométal) in Belgium are discussed: (I) Residual low quality acid and caustic are used in the processing of zinc industry cements to produce copper, nickel, cobalt and zinc concentrates by several consecutive selective leach - precipitation processes.(II) Copper anode slimes are treated and their precious metal contents are recovered. Depending on the composition of the slimes, separate or combined concentrates of copper, bismuth, tellurium/selenium and silver/precious metals can be produced."

Jan 1, 2008

By M. Drozd

Multi-use pad operators require an efficient and economic method to destroy cyanide in their process residues so new material can be stored on the pad and leached. Operators of the dedicated or single-use pads require an effective cyanide destruction method for pad closure. Cyanide destruction can be accomplished by utilizing oxidants such as hydrogen peroxide or calcium hypochlorite, or by utilizing ferrous sulfate which sequesters the cyanide in strong acid dissociable complex. Ferrous sulfate can be the preferred method of cyanide destruction because it is a less costly chemical, reaction rates are almost immediate and unlike oxidants, it can penetrate the total depth of a pile without being destroyed by side reactions. Literature indicates that the (Fe(CN)6)-4 com~lex is produced slowly but it appears that complexes such as Fe(CN)4(H20)2-or Fe(CN)4(OH)2)-4, are formed quickly and should have no U.V. sensitifity, unlike (Fe(CN)6)-4. Stoichiometry of the testwork indicates that Fe«CN)4(OH)2)-4 complex may be the species formed. The usage of ferrous sulfate has the advantage of being able to bring ~ level down that divalent metal ions such as Cu++, Cd++, Hg++, Pb++ and Zn will form insoluble complexes and precipitate from solutions does not destroy weak acid dissolvable complexes and can leave a heavy metal problem behind after cyanide destruction.

Jan 1, 1990

By Li Qihou

Mono-disperse ZnS and CdS nano-particles were prepared by the homogenous precipitation method and the effects of SO42-,NO3- and Cl-ions on crystalline of particles were investigated experimentally. The results showed that these anions had no influence on the crystalline of ZnS, but different crystalline CdS ultrafine particles were produced in different anion systems, where the blend-type CdS was obtained from natrate or sulphate solution, and wurtzite-type CdS from chloride solution. It was ascribed to the coordination of Cl- and Cd2+ that altered the supersaturation of precipitate ions in the solution, the existing growth units and their connecting patterns, thereby producing wurtzite-type CdS with a more stable structure.

Jan 1, 2006

By R. Cheng

The kinetics of the solvent extraction of ythium from HCl solution with mono-2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester (HEHEHP) have been studied using a rotating diffusion cell (RDC). The effects of rotation speed, pH, ymium and extractant concentrations and temperature on the rate of extraction were examined. The rate of extraction of ythium appears to be controlled by an interfacial reaction of metal ion and extractant. The concentration of the latter is determined mainly by diffusion through the membrane. The contributions of the rates of diffusion in the diffusion layer, diffusion in the membrane and chemical reaction at the interface to the overall rate have been calculated on the basis of a kinetic model.

Jan 1, 1992

By Sung-Mo Jung

Experiments were carried out on a system with artificially prepared slags in a graphite crucible, in order to examine the possibility of recycling BOF slags produced in the steelmaking process. More than 80% of FeO and P2O5 was reduced within 20 minutes and the FeO reduction rate was greater than that of P2O5. P2O5 reduction began after more than 60% of FeO was reduced. Increasing slag basicity enhanced the reduction of FeO and P2O5. Temperature also improved slag reduction. The overall reduction rate was controlled by the chemical reaction at the slag/carbon interface. The reduction rates of FeO and P2O5 were second and first order with respect to their respective contents. Most of the reduced phosphorous is believed to vaporize in the form of P2 gas.

Jan 1, 2006