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By Ibrahim Yusufoglu, Cem Kahruman, Sedat Ilhan, Ahmet Orkun Kalpakhi

"Scheelite is the main raw material in tungsten production. In hydrometallurgical processes, extraction of tungstate ions into solution is very important. During the leaching of scheelite in oxalic acid solutions, tungsten dissolves as a chelate complex. Scheelite includes impurities along with calcium tungstate. Determination of the dissolution of these impurities is important in the subsequent tungsten production stages. In this study, scheelite was dissolved in oxalic acid solutions and the dissolution of impurities was investigated. The quantities of dissolved impurities were determined by ICP - OES and characterization of the undissolved impurities in the leach residues was carried out by SEM - EDS analysisIntroductionScheelite and wolframite ores are used for the industrial production of tungsten. Both ores are dissolved in acidic or basic solutions, and ammonium paratungstate is obtained as an intermediate product. Prior to crystallisation of ammonium paratungstate, all the impurities must be removed. Among these, Fe, Si, P, Mn, Mg and Mo are classified as ""harmful"" elements and different methods are used for their removal [1]. During purification, solvent extraction, ion exchange, etc. methods are used.Potashnikov et al. [2] studied the dissolution of scheelite in acidic solutions and the effects of stirring speed, temperature and oxalic acid concentration on the dissolution kinetics.There are no works in the literature about the removal of impurities from scheelite ores in oxalic acid solutions. Therefore, the aim of this work was to investigate the dissolution mechanisms of impurities during the leaching of scheelite in oxalic acid solutions. The effects of temperature and oxalic acid concentration on the dissolution were also investigated. In addition, the characterization of the impurities which were not dissolved was studied."

Jan 1, 2012

By Jens Kristen Laursen

In 1999, Molymex S.A. de C.V. (Molymex), Mexico. (a company wholly owned by Molibdenos y Metales S.A. (Molymet), Chile) decided to install the Haldor Topsrae Wet gas Sulphuric Aicd (WSA) process for cleaning of the 4-5% SO2 off-gas from their molybdenum sulphide master in Cumpas, Mexico to produce sulphuric acid. The decision to install a WSA plant was based on the successful operation of a WSA plant at Molymet's molybdenum sulphide roaster in Santiago, Chile since 1993. This paper describes the process layout of the Cumpas plant, the operating experience of the Santiago plant, and the, differences in. process design between the two plants. It will furthermore summarise the applications of the WSA process for other roasting plants and smelters within the non-ferrous. metals industry producing metals such as copper, lead, and molybdenum.

Jan 1, 2002

By Wander. L. Vasconcelos, Virgínia. S. T. Ciminelli, Angela. M. F. Guimarães

"The present work was aimed at synthesizing nanostructured hybrid materials derived from the functionalization of smectite clays with ligands containing thiol (-SH) groups for application in cadmium adsorption processes. An in nature Brazilian bentonite was investigated. The modification route was based on the grafting reaction between hydroxyl groups present on clay surface and the hydrolyzable alkoxy group of the (3-mercaptopropyl)trimethoxysilane in dry toluene under reflux. The present work showed that the proposed modification route was effective for the grafting of the thiol groups in the clay structure. The thiol-functionalized bentonite samples showed average binding capacities 160% higher with respect to Cd2+ to those obtained with the ungrafted material. These results support a mechanism of adsorption involving primarily ion complexation by the thiol groups (specific) instead of cation exchange (unspecific). The proposed modification processes are suggested for the preparation of novel adsorbent materials with controlled selectivity and specificity and therefore with good potential for separation and pre-concentration purposes.IntroductionMany efforts have recently been devoted to the design and preparation of inorganic-organic nanomaterials because of their potential application in novel functional materials. The intercalation of organic species within the spaces between interlayers of inorganic layered crystals provides nanostructures consisting of alternating layers of inorganic and organic compound. The intercalation reactions occur by insertion of mobile guest species (neutral, molecules, or ions) into the accessible crystallographic-defined vacant sites located between the layers (interlayer spacing) of the layered host structure [1}.Silane coupling agents, used widely for the modification of silica surfaces, have also been employed more recently for modification of layered silicates [2,3,4,5]. Modification with organosilane involves grafting reactions by establishing covalent bonds between the reactive groups of the layer, normally hydroxyl groups, and silane molecules. These reactions can be restricted to the external surface (the basal spacing remains unchanged) or to the interlayer surface, in which case an interlayer expansion occurs. The resulting material can be defined as a hybrid material or, more specifically, functionalized inorganic layered material [1]."

Jan 1, 2008

By Eliezer Martinez-Jimenez, Gretchen T. Lapidus

"Electro-assisted reduction is an effective pretreatment to render chalcopyrite less refractory towards oxidative leaching. In this process, chalcopyrite is selectively converted to chalcocite or copper metal in an electrolytic cell under ambient conditions, while ferrous ion is leached into solution. However, the reaction velocity is hampered by the formation of a ferrous sulfide passivating layer on the solid surface, especially at elevated solid to liquid ratios. In the present work, several strategies for overcoming this problem were evaluated. On one hand, specific ligands for ferrous ion were added in order to increase its solubility and, on the other, an anode material which promotes the oxidation of the sulfide ion was chosen. Leaching tests showed citric acid to be an effective ligand for both ferrous and ferric ions and, in combination with a lead-silver anode, significantly increased the kinetics of chalcopyrite reduction and subsequent copper leaching.IntroductionAttempts to oxidize chalcopyrite at a rapid rate in aqueous solutions, below their normal boiling point, have met with difficulties because of passivation by some of its own components. An alternative line of research explores reductive pretreatment, transforming the chalcopyrite into less refractory copper phases, which can later be oxidized. A recompilation of these efforts up until 2000 was published by Dreisinger and Abed [1]. However, this practice usually requires large excesses of reducing agents, such as copper, lead, aluminum or iron, and in this last case at near-boiling temperatures, in highly"

Jan 1, 2012

By Alireza Zakeri

To evaluate the behavior of minor elements in the copper smelting process, activities of silver, selenium and tellurium at minor concentration were determined at 1473 K within the miscibility gap of the Cu-S-Me (Me = Ag, Se, Te) and Cu-Fe-S-Me systems varied in Fe/Cu ratio. Phase relations between the immiscible metal and matte phases in the foregoing systems were first established by a quenching technique at 1473 K to supplement the activity measurement data. A Knudsen-effusion mass spectrometer, capable of handling complex gaseous systems and relatively small vapor pressures, was adopted for activity determination. Using a multiple Knudsen-cell, the ion intensity of minor element in the sample under study was measured simultaneously with that in a reference sample. Activity was obtained from the ratio between the measured ion intensities as well as the known activity value of the minor element in the reference sample. Limiting activity coefficients of the minor elements were correlated with composition of the matte. Based on the experimental results, the vaporization behavior of the minor elements has been discussed.

Jan 1, 1999

By L. Salinas

Lance injection of gas and particles into a molten bath is currently practised in metallurgical processes (Mitsubishi lances for example). Several experimental and theorical studies have been conducted in the past on this topic. However, neither detailed calculations nor experimental studies of local flow patterns have been published. In the present work, a numerical simulation of the interaction of a gaseous vertical descending jet and a liquid surface was done, using the turbulence k-e model. There is a fair agreement between the calculated and the experimental values. The results of this study demonstrate that it is crucial that the gas jet velocity profile and turbulent characteristic are correctly formulated in order to correctly simulate the system.

Jan 1, 1999

By A. K. Kyllo

The use of Composite Furnace Module cooling systems has been shown to give improved refractory performance in a number of above bath locations in WMC flash furnaces. To test the behaviour of modules in contact with a melt, a set of instrumented modules have been installed in the reaction shaft of a. nickel flash furnace. The location was chosen to provide a suitably harsh environment to ensure rigorous testing, while still allowing relatively easy access for module installation. The modules were continuously monitored to provide information on the module performance, as well as the temperature in the shaft itself. The shaft temperature showed significant transient behaviour, which resulted in heat fluxes through the modules ranging from 10 to 92 kW m-2. The modules were capable of handling the highest heat flux with no risk of the coolant boiling. This paper details the design and operation of the modules over a period of seven weeks.

Jan 1, 1999

By Wen-Ming Chien

Low temperature X-ray diffraction and thermal property studies of the solid-solid state phase transition for the polyalcohols (pentaerythritol (PE), pentaglycerine (PG) and neopentylglycol (NPG)) thermal energy storage solid solutions have been investigated by using X-ray diffractometry and differential scanning calorimetry (DSC) methods. X-ray diffraction studies on polyalcohols solid solutions, PE-NPG and PG-NPG, are from ?10oC to 50oC. XRD results shows the + mixed phase at the related low temperature (?10oC) for both PE-NPG and PG-NPG solid solutions. At high temperature range, XRD results show phase for PG-NPG solid solution and + mixed phase for PE-NPG solid solution. There are only two Bragg peaks, (111) and (200), shown in phase XRD patterns. The polyalcohols solid solutions have been cycled 5 times between -20oC to 100oC at different DSC scan rates to study the phase transition properties. DSC results of both PE-NPG and PG-NPG solid solutions show that the solid-solid state phase transition is near room temperature. Details of low temperature phase transition XRD and DSC results of PE-NPG and PG-NPG solid solutions will be presented

Jan 1, 2006

By Takashi Yoshida

"This paper will discuss the recent situation and future of the zinc industry from the technical point of view. It includes recent problems faced by the zinc industry and technological developments. One of the biggest problems of the zinc industry is raw materials. Traditional zinc concentrate becomes much complicated with respect to its chemical and physical properties. Thus, each process faced various problems. Also, secondary resources, generating so called recycling processes, become much more important. Recycling is, of course, a very important aspect for sustainable development of society. Secondary raw material also includes a great variety of impurities not included or very low levels in traditional zinc concentrate. Some problems are caused by these impurities. To overcome these problems some technological challenges have been taking place. Details will be discussed in the symposium.IntroductionZinc is a very useful metal based on its elechtro-chemical, chemical and physical properties. The most important usage is galvernizing of steel which is used for automobile, construction and a very wide range of other indutries. Also, zinc is used for dicasting and other alloys such as brass. Smelting of zinc is different from other metal because of its electro-chemical properties. Many parameters should be controled compared with other metals such as iron and copper. Typical zinc smelting processes are the Imperial Smelting Process (ISP) and the electlolytic process. The ISP process is a pyro-metallurgical process using a blast furnace. The electrolytic process is a hydrometallurgical process. Both processes are energy intensive, and the smelting process cost is increasing because of higher energy costs. The situation of the ISP is very severe because of higher coke prices. Recently, many ISP plants have been shut down because of economic reasons"

Jan 1, 2012

By A. Filzwieser

The highest current density suitable for the electrowinning process is between 50 to 60 % of its limiting current density. One of the most important influences on the limiting current density is the thickness of the hydrodynamic boundary layer near the electrode surface. Therefore, the fluid flow in a copper electrowinning cell is calculated. The numerical simulation - using the CFD-software package FIRE® - considers all three different types of the fluid flow, namely, the natural convection, the forced convection by electrolyte circulation and the forced convection by electrochemically induced gas stirring. The simulation of natural convection is based on the different density values in the boundary layer at the electrode surface given by a density/concentration correlation. The copper concentration - linked with the current density by Faraday law - is solved by an additional transport equation. The simulation of the forced convection by the electrochemically-induced gas stirring is done by using a real two-phase calculation. That means that all differential equations are solved again for the second phase. The numerical solution of the fluid flow field is compared with the results of LDA- measurements, which were done in a special cell. The software for the LDA enabled a calculation of the void fraction possible and therefore a rough estimate of the mass transfer coefficient through the prevailing gas bubble induced convection can be made by assuming the influence of relative bubble volume.

Jan 1, 1999

By Ibrahim Yusufoglu, Ahmet Orkun Kalpakli, Cem Kahruman, Sedat Ilhan

"The effects of oxalic acid concentration, temperature, stirring rate and particle size on the dissolution rate of synthetically prepared calcium molybdate were investigated. Dissolution of calcium molybdate in oxalic acid solutions takes place as a series - parallel type reaction. In the first reaction step, which proceeds according to the ""Langmuir - Hinshelwood Mechanism"", calcium aqua oxalato molybdate is formed as a complex chelate intermediate product. In the second reaction step, molybdic acid is formed during the slow hydrolysis of calcium aqua oxalato molybdate, and it reacts rapidly with oxalic acid to form the polymeric hydrogen oxalate dimolybdate chelate as an end product. Activation energies were calculated as 41.4 and 49.9 kJ mol-1 for the first and zero order reactions. The fractional conversion versus time relationship can be given by the following equation.IntroductionMolybdenum is used widely in electric-electronic, metal working, aerospace and aeronautic, nuclear, glass and petrochemical industries because of its high melting temperature and resistance against chemical effects. However, the largest molybdenum consumers are the iron-steel and super alloy industries where molybdenum is used as an alloying element. Industrially important molybdenum minerals are limited to molybdenite (M0S2), powellite (CaMo04) and wulfenite (PbMo04), which are considered as primary molybdenum resources. Secondary molybdenum resources are spent catalysts and scrap [1-4].Molybdenum has been produced by pyrometallurgical processes in the past. Since it is possible to process low grade molybdenum ores and industrial wastes by hydrometallurgical processes, which are more environmentally friendly than pyrometallurgical processes, the importance of the use of hydrometallurgical processes has increased in the molybdenum production industry."

Jan 1, 2012

By M. E. Ramos Rada

Mexicana de Cobre, which is part of Grupo Mexico, carried out studies for the construction of a copper refinery in the La Caridad Metallurgical Complex located in Nacozari, in the state of Sonora, Mexico. After the studies were concluded, the decision was made to construct a 180,000 t/y refinery using the state of the art permanent cathode Kidd Process. The basic engineering was developed by Fluor Daniel and the detail engineering and the construction were carried out in record time by the Mexican company Bufete Industrial. During the construction phase, Grupo Mexico decided to expand the refinery, and actions were taken to increase its capacity by an additional 120,000 t/y; the final result was a refinery capable of producing 300,000 tonnes of grade A cathode per year. Construction began in January 1996, and the operation of the first stage began on July 1, 1997. The operation of the second stage commenced on January 7, 1998. The capacity of the first stage was reached in November, 1997 and the total capacity of the refinery was achieved in May, 1998. This presentation describes the process and equipment installed in the refinery, the steps leading to the start-up, the operation and the results obtained during the first two years, the handling of anodes with high impurity contents, and the problems confronted and the way they have been solved. It also includes personnel productivity, the control parameters and the most relevant data on the operation of the process.

Jan 1, 1999

By Jingbo Liu, Zhimin Wang, Wenchao Li

"IntroductionThe advantages of non-stoichiometric perovskite material are highlighted in many papers[l]and many of this family of materials are well-suited to integration into microsensor devices. Among them, barium titanate is the most promising due to it's piezoelectric, pyroelectric, dielectric properties. Through modification, BaTiO3-based materials can be utilized in many kinds fields, such as surface wave probe; pholoconducting devices, field-effect transistor, permanent memory permanent storage, and ultrasonic transducerl2-3l. In this Paper, a series of BaTiO3-based polycrystals were synthesized by sol-gel processing which appears to be a very promising method for the manufacture of ceramic, because it offers significant advantages such as high purity, chemical homogeneity, controlled particle sizes of ceramics, and lower processing temperatures [4]. In a sol-gel process, alkoxides of the constituent elements show different reactivity toward water so that the preparation of multi-component homogenous system is difficult. In the experiment, inorganic salt was substituted for some of the alkoxides. Acetic acid which is employed for the solvent and catalyst, acts as donor ligand to titanium alkoxide and controls, the hydrolysis polycondensation reaction. Taking these aspects into consideration, we select the system Ba(OAc)2, , La(OAc)3, Ti(O11Bu)4 and acetic acid which is used as both solvent and homogeneous catalyst for the first time.ExperimentalA series of La3+-doped BaTiO3-based nano-crystals were prepared with sol-gel technology using various parameters. The precursor solution was prepared in the presence of barium acetate, lathanium acetate, and titanium tetrabutoxide monomer in butyl alcohol. According to the flow chart (fig. I.), Ba(OAc)2, La(OAch dissolved in the glacial acetic acid (0. lmol/40ml) in a three-neck flask were mixed with a solution of titanium tetrabutoxide monomer in butyl-alcohol(l 7ml/20ml) at room temperature and under constantly, vigorous stirring conditions. In most cases, the resultant solution was golden yellow and stable in the air. To this precursor solution, containing Ba, La, Ti in the desired ratio, water was added incrementally for hydrolysis under continuous stirring until sol was formed. After aging for more than 2 hours, sol was transformed to gel at room temperature. If heated during aging, the gel was formed in a shorter time. The wet gel was allowed to dry at 50°C for more than 10 hours. The dried gel was transparent or light yellow. In order to obtain BaTiO3-based nano-crystals, the amorphous dry gel was calcined at 600°C, 700°C, 800°C, 900°C, 1000°C respectively[5]. The ceramic humidity sensor was formed through the cold-pressed, aged, capsulated routes. The dried gels were crushed in an agate mortar and then pressed into discs of ? 1.5 X l.5mm (l.5mm diameter and l.5mm thickness), then held at about 16.5 MPa pressure for 3 min [6]. The disc was sintered at 1350°C and 1400°C for I hour respectively. During the processing, an Ag-Pt electrode was inserted in the sensor [7]. (See the flow chart.)"

Jan 1, 2000

By A. A. Bustos

Four Air Liquide Shrouded Injectors (ALSI ) were installed and operated for over one year in a Peirce-Smith converter at the Falconbridge nickel smelter in Falconbridge, Ontario, Canada. A shrouded injector consists of an inner pipe and an annulus, through which high oxygen enriched air and nitrogen flow, respectively The nitrogen cools the injector and protects the refractory in the vicinity of the injector tip, allowing for substantial increases in oxygen flow rates to the converting reactions. Several injector designs were tested to study the effect of changes in the cross-sectional area and changes in the entrance geometry of the annulus. An optimum design would minimize the injection pressure required for a given flow rate to achieve choked flow conditions at the tip of the injector. The operation of the ALSI was simple and did not require any special care or maintenance, either between blows or between converter cycles. In particular, the shrouded injectors did not require punching, as is the case with conventional tuyeres. In terms of refractory performance, the ALSI, operating at 30-40 % oxygen enrichment, were superior or equal to the conventional tuyeres, which operated at 21-23% oxygen. The results of the demonstration program led Falconbridge Limited to implement the ALSI technology on a commercial scale The paper presents the demonstration program results in terms of gas flow rates, accretion formation, punchless operation and refractory wear.

Jan 1, 1999

By Kazuya Koyama

The leaching of copper from a printed circuit board (PCB) and the electrodeposition of copper from a cuprous solution in ammoniacal alkaline solutions were examined in order to develop an energy-saving hydrometallurgical process for copper recovery from electronic scrap. In the leaching experiments, copper in the PCB was oxidized by Cu(II), and Cu(I)-ammine complex ions were formed. The copper(I)-ammine complex slightly depressed the leaching rate, while Cu(II)?ammine markedly enhanced it. During the electrodeposition experiments, the current efficiency of copper deposition was approximately 100% in the current density range of 200 to 1000 Am-2. The electrodeposition of copper from the Cu(I)-ammine complex solution favored the production of plates rather than powders.

Jan 1, 2003

By K:-I. Rhee

The recovery of tellurium from Te-cement obtained during the processing of copper anode slimes was carried out by a series of hydrometallurgical processes, i.e. leaching Te-cement in NaOH solution, precipitation of impurites with the addition of Na2S followed by direct electrowinning of tellurium in NaOH solution. The optimum conditions for each process were determined and discussed in terms of various parameters associated with each step to maximize the recovery and purity of tellurium. The final purity of tellurium from electrowinning in alkaline solution was found to be more than 99.9 %.

Jan 1, 1997

The physico-chemical principles of chloride hydrometallurgy are reviewed to rationalise the complex chemistry in chloride-based processes for metal sulphides in terms of the predicted Eh-log[Cl-] relationships, measured changes in activity of H+, Mz+, Cl- and solubility of Ag(I), Cu(I), Cu(II), Pb(II), Ni(II), Au(III), Sb(III) and Bi(III). These changes reflect the nature of chemical speciation, competing effect of hydration/hydrolysis and chloro-complexation,composite effect of increasing acid and/or salt concentration and decreasing water activity. Rate data for the dissolution of PbS and ZnS in HCl containing Fe(III) or Cu(II) are compared and contrasted to highlight the effect of acid and chloride concentration, water activity, and the nature of oxidant. It is shown that LiCl, NaCl and HCl influence the kinetics of oxidative PbS leaching based on their effect on solubility of PbCl2 co-precipitated with elemental sulphur on the mineral surface. Evidence for the beneficial effect of Cu(II) in sulphide leaching is discussed.

Jan 1, 2003

By S. K. Kawatra

A growing concern for pyrometallurgical operations is the generation of airborne particulates. These particulates can be generated by combustion processes, or by materials handling. Regulation of these particles by the EPA has become progressively more stringent, first for particulates finer than 10 micrometers (PM10), which are particles fine enough to be inhaled into the lungs. Then, restrictions were introduced on emissions of particles finer than 2.5 micrometers (PM2.5), which are fine enough to become embedded in lung tissues. The next stage of regulations is likely to be ?nanoparticulates,? particles finer than 100 nanometers, which are in a size range where their very high surface area leads to enhanced reactivity. While all of the health effects due to nanoparticulates have not yet been determined, there have been enough studies to indicate that there is a problem, and restrictions on nanoparticulate emissions are only a matter of time. In this paper, it will be demonstrated that dry handling, comminution, and combustion sources represent a significant concern for both PM and nanoparticulate emissions. In regards to dry handling, the effects of utilizing effective dust suppressants on PM and nanoparticulate emissions will be explored.

Jan 1, 2006

By John Jiang, Yeonuk Choi, Olivia Wang, Gus Van Weert

"As part of a general review of processing double refractory ores through Barrick Gold's autoclaves/CIL facility at Goldstrike, Nevada, blanking the gold cyanide adsorbing native carbon in the ore with hard (m.p. >55°C) paraffin wax was proposed. To avoid interference from other ore constituents in the exploratory testwork, commercial activated carbon was substituted for native carbon in the ore to establish the best conditions for de-activation of carbon with molten wax.IntroductionDouble refractory gold ores present two barriers to gold extraction. The first is generally a physical barrier: the gold is encapsulated or dispersed in a matrix which is impervious to the gold lixiviant. In most cases, including the Goldstrike deposit, this involves a pyrite or arsenopyrite matrix, although minor gold may also be dispersed in competent silica (quartz) or iron oxides. Gold can be rendered accessible by oxidative destruction of such sulphide matrices. At Goldstrike this is practised by roasting and autoclave oxidation (POX). It is the latter route to which this paper refers.The second barrier refers more correctly to gold recovery. Gold may be extracted from the autoclave oxidized solids with cyanide, forming a gold cyanide complex. One characteristic of this complex is that it adsorbs on graphitic surfaces. This behaviour is used advantageously on a large scale by gold millers, who use man made activated carbon particles to remove the gold from solution during leaching: the Carbon-In-Leach, or CIL process. The gold bearing carbon particles are larger than the ore solids and can be separately recovered by screening. Goldstrike uses the CIL technology to recover gold after autoclave oxidation."

Jan 1, 2012

By A. N. Lasseigne

Hydrogenation behavior of the NaAlH4 intermetallics is investigated utilizing thermoelectric power and magnetic analyses. Using both thermoelectric power and magnetic susceptibility measurements on these intermetallics allows for confirmation and further insight into hydrogen's role in altering the material's electronic structure. The electronic and magnetic property correlations will indicate the direction for further alloy development to optimize hydrogen storage.

Jan 1, 2006