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By K. S. Barros, D. C. R. Espinosa, J. A. S. Tenório

Over the past several decades, electrodialysis membranes have been employed for the removal of metals from galvanizing industry effluents. However, for its technical viability, it is useful to know some properties of the system to avoid, for example, precipitation of inorganic salts, destruction of the membrane and an increase in the energy consumption. The scope of the present study is to use chronopotentiometry to determine limiting current densities, transition times and resistances of the cationic membrane HDX 100 using a synthesized solution of the galvanizing industry effluent prepared with copper sulfate and sulfuric acid in different concentrations: 0.1, 0.5 and 1.0 g/L of Cu +2. The current-voltage and chronopotentiometric curves obtained have clearly defined regions and it was verified that the Cu+2 concentration causes a significant increase in the limiting current densities and in transition times. However, a high decrease in resistance occurred because at the highest concentrations, it is more difficult to reach the zero concentration value at the membrane surface. Besides, the pH increase causes a significant decrease in the limiting current density and in the transport number, but a slight increase in the resistance due to the presence of hydrogen. The results obtained confirm that the chronopotentiometry method is a valuable tool to determine membrane properties.

Mar 1, 2017

By Seetharama C. Deevi, Mohammad R. Hajaligol, Sarojini Deevi

"Carbides and nitrides of iron are being considered as magnetic materials for high-density recording due to their chemical stability and high-saturation magnetization values (> 100 emu/g). Iron carbides and iron nitrides with magnetic properties suitable for magnetic media were synthesized by employing a novel synthesis procedure based on fluidization of powders in reactive atmospheres. Fluidized-bed reactors of laboratory, bench, and pilot scale were employed for the synthesis of iron carbide, FeSC2, by reducing and carburizing U-Fe203 in the temperature range of 300 to 550 ºC. A temperature of 400· ºC and a reaction time of 2 to 3 h are found to be optimal for the synthesis of iron carbide. When the carburization was carried out in a reducing and carburizing atmosphere such as carbon monoxide, nucleation and growth of FeSC2 occurred directly from Fe304 with no intermediate phases such as FeO or Fe. Longer carburization times resulted in the deposition of carbon on the surfaces of FeSC2 particles due to Boudouard reaction, and higher temperatures favored the formation of a mixture of carbides such as FesC2 and Fe3C. Iron nitrides were synthesized by reducing u-Fe203 in the temperature range of 350 to 550 ºC, followed by nitriding in the temperature range of 350 to 550·ºC. The powders were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analyzer, and a vibrating sample magnetometer.IntroductionRecent demand for high-quality recording of optical, electrical, and audio signals generated interest in magnetic tapes with high-recording densities as compared to the conventional magnetic tapes based on U-Fe203. At present, commercially available magnetic tapes contain maghematite, U-Fe203, as a magnetic material with a saturation magnetization of90 emu/g and a coercive force of 400 Oe. Recording of signals at a higher density per unit volume of magnetic material demands magnetic materials with high-saturation magnetization and a reasonable coercive force. Although metallic iron particles possess a saturation magnetization of 130 to 150 emu/g and a high coercive force of 1000 Oe, the gradual oxidation of iron-to-iron oxides (of lower saturation magnetization) prevents the use of iron particles for high-density recording. In contrast, iron carbides such as FesC2, Fe7C3 and iron nitrides such as Fe4N and Fe3N possess excellent magnetic properties coupled with good electrical conductivities and high hardness. The carbides and nitrides of iron have generated significant interest as magnetic materials for the next generation of magnetic tapes due to their unique magnetic properties and relatively greater oxidation resistance as compared to metallic iron particles [1-4]."

Jan 1, 1994

By T. T. Chen

Gold in the Twin Creeks ore is primarily associated with arsenian pyrite. During pressure oxidation, the sulphides are solubilized, but part of the dissolved iron reprecipitates as jarosite and as an iron sulphate-arsenate-phosphate phase. The pressure oxidation products are subjected to cyanide leaching. The cyanide leach residues consist of quartz, gypsum, bassanite, anhydrite, small amounts of jarosite, an iron-sulphate-arsenate-phosphate phase, as well as trace amounts of orthoclase, rutile, pyrite, hematite and monazite; all these particles are dispersed in a fine grained matrix of illite-muscovite. The autoclave leach residues contain a small amount of carbonaceous matter. Many gold grains are detected on the surfaces of the carbon particles, and these gold particles are not leached during cyanidation. The gold particles are typically 0.1-0.2/Lm in size and commonly are embedded in the carbon surface or are coated with a K-AI-Si-S-O phase on the surface of the carbon. The gold grains are consistently associated with elevated CI contents (50-300 ppm Cl). The poor gold cyanide leach recoveries, which initially occurred in the Twin Creek developmental circuit under certain operating conditions, are attributed to the presence of chloride in the feed. This results in the formation of soluble gold chlorocomplexes in the autolcave and the subsequent sequestering of the gold on the surfaces of the carbon particles.

Jan 1, 2000

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as sulphuric acid or liquid SOz, On the other hand, natural gas may contain over 20% of hydrogen sulphide (HzS) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert SO2 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By Bruce Cavender

Managers are frequently faced with the decision to perform a task or manufacture an object in-house or to hire an outside vendor to perform the function. Outsourcing decisions are usually driven by economics: work is outsourced if it can be completed at a lower cost or in a shorter time than it can in-house. A technique termed incremental analysis can be used to make this decision. Incremental analysis examines the financial impact of outsourcing decisions as a function of the firm's fixed and variable operating costs. To use this tool, individual components of production cost are identified as being either constant or varying with levels of production activity. The assignment of cost type can be made in several ways: though analysis of historical operating data, understanding of individual expense types, and so forth. Changes in fixed and variable costs resulting from each potential course of action are explicitly identified to project the financial outcome of each alternative. The alternative having the greatest positive impact on profit is selected for implementation. By using the fixed- and variable-cost framework, the analysis is conceptually straightforward and substantially simplified. Production managers can therefore use incremental analysis as a tool for fast economically beneficial decisions on a real-time basis.

Jan 1, 1999

By V. L. Stolyarova

The high-temperature Knudsen effusion method was used to study partial pressures of vapour species, activities of components and the Gibbs free energies in the DyF3-Dy2O3 system at the temperature (1357±5) K. Partial pressures of vapour species were obtained by the ion current comparison method, with the DyF3 partial vapour pressure over pure DyF3 as a standard. The equilibrium constant of the gaseous reaction DyF3 + DyOF = Dy2OF4 is evaluated. Thermodynamic data obtained are in a agreement with the available phase diagram of the DyF3-Dy2O3 system. Results of the present study illustrate the negative deviations from the ideal behaviour in the system.

Jan 1, 1997

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Wanderson Silva Rodrigues, Paulo Adão Marinho dos Santos, José Antonio Silva Souza, Luis Alves Venancio, Emanuel Negrão Macedo

"1 AbstractThe production of alumina from bauxite using the Bayer process generates 0.7 to 2.0 ton of the residue known as red mud per ton of alumina. This material has no large scale current use and is usually stored. This paper shows that it can be used in a suspension with water as a gas effluent cleaner with high efficiency to remove SO2. It can substitute other materials currently used reducing the overall environmental impact and potentially reducing the cost of gas treatment.2 IntroductionThe production of millions of tons per year of alumina around the world generates from 0.7 to 2.0 ton of the residue known as red mud per ton of alumina. The vast majority of the red mud is stored in large sealed lakes. Due to the high reactivity this material is considered dangerous and currently there is no operating process capable of reuse all the material produced at any refinery. These lakes after filled of solid material eventually have the surface revegetated. In any cases they will remain as an environmental passive and need monitoring for decades. The search of industrial processes that combine the cleaning of gas effluents emission and reuse of these residues can contribute to the reduction of the overall impact of the alumina production process.The main objective of this work is to study the efficiency of the red mud as alternative raw material for the control of emissions of SO2 in combustion gases. Usually this is made through alkaline solutions of CaCO3 or NaOH in absorbing equipments like spray towers or packed column. This project main objective is to study the reaction of the SO2 with a suspension of red mud and water in order to obtain the basic parameters to design equipment capable of process this reaction on a pilot scale. With that goal compositions of red mud on spray were processed with flow of gas containing SO2 with concentration similar to the exhaust gases of the combustion process of the refineries."

Jan 1, 2011

By Omid Marzoughi

In this research, both the kinetics and the mechanisms of the roasting of a sphalerite concentrate from the Bafgh mining complex in Iran were investigated. The oxidation process was performed in a muffle furnace in air and the effects of time and temperature on the degree of oxidation of the zinc sulfide sample were quantitatively studied. The experimental data were fitted to the shrinking core model. In the temperature range of 650–800 °C, the rate-controlling step was the chemical reaction between the zinc sulfide and oxygen with an activation energy of 103 kJ mol−1. On the other hand, in the temperature range of 850–950 °C, the rate-controlling step was oxygen diffusion with an activation energy of 50 kJ mol−1. Also, the roasting process was studied using thermogravimetric (TGA) and derivative thermogravimetric (DTGA) techniques.

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

By Pier-Lorenzo Solari, Philippe Moisy, Michel Schlegel, Stephane Pellet-Rostaing, Eric Mendes, David Bengio, Richard Husar, Thomas Dumas

Ionic liquids (ILs) are molten salts composed of an organic cation that are liquid below 100 °C. They demonstrate unique physico-chemical properties such as good conductivity, negligible vapor pressure and non-flammability. As a consequence, they are often regarded as green solvents and could become an alternative to the use of both high-temperature molten salts and volatile organic solvents in rare-earth elements processing and recycling. The diversity of interactions existing in an ionic liquid allows the solubilization of both polar and apolar compounds. Moreover, coordinating functions on their composing ions can lead to stabilization of some species. For instance, in non-aqueous media, europium exists in the (II) oxidation state which is not stable in aqueous solutions. Understanding the mechanism of Eu(III) electrochemical reduction to Eu(II) and the stabilization of Eu(II) species in IL media could be of major interest for the development of innovative recycling processes. Using transient electrochemistry and UV-Vis spectroscopy we could get valuable information on the redox behavior of the Eu(III)/(II) couple in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIm][NTf2]). Reduction of Eu(III) to Eu(II) and stability of Eu(II) was also studied thanks to a XAS-spectroelectrochemistry set up used to follow in situ the evolution of the XANES spectrum around the L3 edge of Eu during electrolysis.

Mar 1, 2018

By U. Meyer, A. Alonso, P. Banios

The sampling of cathodes has changed with the introduction of the ISA-process in copper refineries. A Jernkontoret joint working group of refineries and rod plants from both primary and recycled copper plants has been investigating whether the actual sampling of cathodes is representative for this type of cathodes. As a first stage, samples were sent to the members of the working group with the objective to find an easy basis for a comparison of the results of the next stages. All samples show the same tendency for nearly all elements. In some cases, there may exist differences in calibration and for some elements the detection limits are too high, especially when Optical Spectrometry is used. In the second stage, discs were compared with melted samples to answer the question whether the punching of discs is sufficient for the quality control of the cathode. The analyses of the discs represent fairly well the cathode quality. There are differences between cathodes from different crops. Three punches are sufficient to determine the cathode quality. Finally, samples from various lots of cathodes were compared with samples from the rod produced from these cathodes. The impurity content of the rod corresponds to the impurity content of the cathode.

Jan 1, 2000

By R. V. Kumar

"The use of sensors to monitor gaseous species in industrial processes is discussed. All of the existing systems have disadvantages. Sensors, based upon solid electrolytes, which can be placed directly into the gas stream are attractive but many also respond to oxygen, need to be sealed at high temperatures and require a separate reference. This paper describes sensors, usually based upon two electrolytes, which do not respond to oxygen and do not require high temperature gas seals or separate references. The application of these sensors to the measurement of carbon dioxide, sulphur dioxide and trioxide and hydrogen chloride is described. These sensors can be placed directly into the gas stream at elevated temperatures.IntroductionOn-line gas sensing is becoming more important as concerns regarding the environment mount. There are many established techniques for monitoring gases in industrial processes, with applications in safety monitoring, chemical analysis or process and emission control. Flue gas analysis involves the greatest technical complexity, requiring several sophisticated capital-intensive spectroscopic instruments for different species as well as needing highly skilled operators. There are also several instruments, based upon aqueous electrochemistry, which are available for the analysis of the gases S03, S02, N02 but these require that the gases are sampled at high temperature and cooled, prior to analysis. These instruments cannot be considered as giving on-line measurements of the gas composition. Furthermore, the power requirement of these instruments frequently precludes battery operation for field and domestic use."

Jan 1, 1997

By W. G. Davenport

This chapter examines three minor influences on flash smelting's industrial oxygen and oil requirements, i.e.: (a) recycle of molten converter slag to the flash furnace (b) gangue oxides and carbonates (e,g, Ah03, CaC03) in the flash furnace feed (c) minor sulfides (e.g. NiS} in the flash furnace feed. It then examines the. sensitivity of our flash furnace calculations to previously ignored aspects of smelting chemistry -Cu, S and Fe304 in slag and 0 in matte.

Jan 1, 2001

By P. Kerr

Iron segregation is pre-dated by copper and nickel segregation processes for which the experimental methodology and reaction chemistry were established. The accepted reaction sequence for segregation involves the generation of hydrogen chloride, the chloridization and volatilization of the metal chloride, and precipitation of the metal from the metal chloride in the vicinity of carbon. Iron segregation roasting offers a potential extraction solution for processing oxide deposits with complex mineralogy or waste streams such as Minette-type iron deposits, nickel laterites, ilmenite, red mud, electric arc furnace (EAF) dust, mill scale and slag. After subsequent magnetic separation, one is left with a high grade metallic iron powder which can be marketed for powder metallurgy or briquetted to serve as a direct reduced iron (DRI) product. The non-magnetic product is typically concentrated oxides including rutile, alumina, or oxides of V, P, and rare earths, etc. that may be economically recoverable with subsequent processing. While operating conditions vary for different metals, they share the requirements of an elevated operating temperature and a mixture of oxide ore, carbonaceous additive and a chloride additive in varying amounts all in a closed reactor to allow for reducing conditions and contain the volatile chlorides. This process is then followed by some form of physical separation. Testwork performed by the authors shows promising results that may aid in future development of the process. Segregation roasting of iron will likely never displace traditional beneficiation and ironmaking technologies; however, it has great potential in niche markets where traditional technologies have failed or current technologies generate substantial waste.

By Jan A. Aune

The paper describes a number of electric furnace equipment modules especially developed or modified for slag furnace applications. Both the resulting design concept for a modern electric sulfide smelter and some of the changes in traditional process-concepts made possible are outlined.

Jan 1, 1983

By A. Yudiarto, M. Z. Mubarok

At the present paper, synthesis of magnesia from ferronickel smelting slag is discussed. The first stage was extracting magnesium from the slag by leaching in HCl solution. Magnesium extraction of 97% was obtained from the slag leaching with HCl 8 molar, solid:liquid ratio 1:40 (g/ml) and temperature 80 °C after 24 h. Solution purification was performed by adjusting solution’s pH at 95 °C with addition of MgO powder. At pH range range of 3–4, co-dissolved iron was removed as akagenite (b-FeOOH) precipitate. Dissolved nickel precipitation was detected at pH range of 4–6, while dissolved Mg and Al started to precipitate in the forms of pyroaurite (Mg6Fe2CO3(OH)16∙4H2O) and hydrotalcite (Mg6Al2CO3(OH)16∙4H2O) at pH range of 8–9. High purity of brucite (Mg(OH)2) was obtained by Mg precipitation at pH range of 11–12, under stirring speed of 300 rpm and stirring time of 4 h. Calcination of brucite at temperature of 1000 °C completely converted brucite to periclase (MgO) powder after 240 min.

Mar 1, 2017

By Ying Wang, Min Chen, Cuihuan Huang, Haohua Deng, Nan Wang, Ming Chen

Adding limestone directly into converter is considered to be favorable to energy conservation and emission reduction by transferring the decomposition reaction of limestone from the shaft or rotary kiln to the converter. In this paper, the kinetics of limestone decomposing in early converter slag was studied at 1300–1400 °C, and the effects of slag temperature and stirring speed introduced to the slag bath were examined. The kinetic results based on shrinking core model analysis showed that the limestone decomposition was a mixed rate control of chemical reaction and heat conduction through the lime layer, which could be promoted at higher slag temperature by supplying more heat to the converter bath. In addition, the chemical reaction rate constant and effective thermal conductivity were determined.

Mar 1, 2018

By Shangshu Li, Xionggang Lu, Xingli Zou, Zhongya Pang, Kai Zheng, Yinshuai Wang

Metal carbides (MCs), especially transition metal carbides have attracted a lot of attention due to their unique properties, such as high strength and hardness, good chemical and thermal stability. In this paper, a new route was proposed for preparing TiC nanoparticles directly from TiO 2/C precursor by using solid oxide membrane (SOM) technology in molten CaCl2. The TiO2/C pellet pressed under 8 MPa was used as the cathode, and a yttria-stabilized zirconia (YSZ) tube filled with carbon-saturated liquid tin was served as the anode. This process employs an inert SOM to separate the anodic reaction area from the molten electrolyte to control the electrolysis process. The electrochemical process was carried out in molten CaCl2 at 1000°C and 4.0 V from 0.5 to 4 h. The characteristics of the phase composition and morphology of the electrolysis products were investigated. The product electrolyzed was examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy dispersive spectrometer (EDS). The results show that TiC nanoparticles can be obtained directly from TiO2/C mixture at 1000 °C, 4.0 V and for 4 h in molten CaCl 2 and the current efficiency is calculated to be 74.1%. In conclusion, we suggest that the SOM process is a promising environmentally friendly and low energy costs electrochemical method for the facile and controllable electrodeoxidation of MO x/C precursors to micro/ nanostructured MCs.

Mar 1, 2018

By Sebastiaan Peelman

NdFeB permanent magnets are the best available magnets used in many technology applications. However, at their end-of-life (EoL) most of magnets and the contained REEs are lost during the recycling of the bulk metals. The REEs are classified as the most critical raw materials in the European Union, and recycling of REEs from EoL products will reduce their criticality and contribute to the sustainability of REE. Various technological routes have been reported, but most of the methods are effective for highly concentrated magnets or magnet scrap, which is greatly dependent on expensive pre-dismantling processes. This paper presents various innovative metallurgical solutions to the effective REE recovery from current industrial practice for WEEE recycling, including the ferrous scrap from WEEE shredder products and shredder residues from computer hard disk drives. Both hydrometallurgical and combined hydro- and pyrometallurgical REE recovery routes are developed after demagnetization and physical upgrading.