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By Manoj Kumar, Vinay Kumar, Nikhil Dhawan, Manish Wadhwa

"Electronic waste (e-waste) is a collective name given to discarded electronic devices such as Television, Cellular Phones and Personal Computers. Among the heterogeneous metals present in the e-waste are the base metals: copper, aluminium, nickel, tin, zinc, iron and precious metals: gold, silver, palladium, platinum apart from several hazardous and halogens metals. Hence there is a need to recover these metals from electronic scrap by recycling and then re-use, which can meet large amount of metals demand. Hydrometallurgical processing was employed for the recovery of metals from television printed circuit board (TV PCB). Different lixiviants such as hydrochloric acid, Sulphuric acid, and nitric acid were used to understand the dissolution behavior of copper, iron and lead present in the TV PCB. Effect of increasing concentration of nitric acid was also studied. Selective recovery of tin over 95% in the form of tin oxide was precipitated. The precipitated tin oxide was identified by X-ray diffraction technique. Tin oxide of purity more than 99.9% was obtained.IntroductionThe electrical and electronic industries comprising computers, television, mobiles, etc, which are manufactured utilizing printed circuit, boards, capacitors, resistance, soldering material etc. During production, at the end-of service life and degradation due to the advanced version with latest features generate valuable metallic and non-metallic constituents. European Union Council on waste electrical and electronic equipment (WEEE) has classified these into different categories as listed in Table 1 [Streicher-Porte et al., 2005]. Among these the information technology, telecommunications and consumer equipment constitute electronic waste (e-waste) [EC, 2002]. Almost all e-waste consists of an integrated part of printed circuit boards which is a valuable source of several metals such as copper, tin, lead, aluminium, iron, silver, gold, platinum etc. [Relay et al., 1990]."

Jan 1, 2008

By Guo Gongyi

An extraction chromatography by which 99.99 % pure scandium oxide can be prepared from the starting materiel containing about 70% scandium oxide has been developed by taking advantage of some peculiar properties of the complex chemistry and extraction chemistry of scandium. The purification of scandium was performed at room temperature with relatively fast rates in two chromatographic columns. The preliminary separation of scandium from impurities was done by extraction chromatography using tri-butyl phosphate as the stationery phase in the presence of citric acid, and the nearly complete separation in the presence of perchloric acid. The scandium recovery was greater than 90 %.

Jan 1, 1989

By Shivendra Sinha

Total pressure oxidation (TPOX) is widely outreached leaching practice for base metals from sulfide minerals, wherein high temperature (T ∼ 200 °C) and oxygen pressure (pO2 ∼ 25 bar) are required. These aggressive conditions intensify the oxygen mass transfer, and therefore facilitate metal dissolution. However, challenging-cum-negative aspects of such practice are energy and material intensive requirements and high oxygen demand. Thus, the present study explores the novel emulsified medium for enhancement of oxygen mass transfer, which assists faster metal dissolution at significantly lower temperature and pressure condition. It is possible to achieve quantitative dissolution (>95%) of Cu, Ni and Co from mixed sulfide minerals at T ∼ 95 °C and pO2 ∼ 2 bar using an emulsion of 2.5% (v/v) n-Hexadecane in dilute sulfuric acid. In addition, n-Hexadecane was found to be inert, stable and immiscible in a pressurized leaching system, thus can be easily separated and recycled in subsequent leaching stages. Thus, this study offers an energy efficient route for low temperature-pressure leaching of sulfides.

By Noritaka Horii, Katsuyoshi Kakinuma, Hiroshi Yamamura

"ZrO2 and Y2O 3-doped ZrO2 gel film were obtained by spin coating of sol from Zr-n-propoxide, n-propanol, acetylacetone, nitric acid, and water on a silica glass as a substrate. ·Dried gel films crystallized to monoclinic, tetragonal, cubic and their mixed phases, depending on the chemical composition of sol, .firing temperature, and coating cycles. ZrO2 films with highly preferential orientation were successfully obtained from a solution containing a large amount of n-propanol. The highly oriented ZrO2 film was found to have high transparency compared with non-oriented 'films. Electrical conductivity of 8 mol% Y2O 3 doped ZrO2 film was also measured.Introduction3 mol% Y2O 3 doped ZrO2, which has a tetragonal symmetry is ·well known to have a strong mechanical property and a high toughness. (1) On the other hand, 8 mol % Y 2O 3-doped ZrO2 is high oxide-ion conducting material and is applied to oxygen sensor, oxygen pump, and solid oxide fuel cell (SOFC). (2) Sol-gel methods using metallic alkoxide are widely applied for synthesizing ceramics such as high-purity fine particles, thin film, and fiber. (3) For ceramics films, many reports have been made on SiO2, (4) TiO2, (5) and PZT. (6) Several case studies have been done on zirconia film based on the sol-gel method, (7) - (11) but very few on preferentially oriented film and on systematic Y zO3 doping. Almost zirconia ceramic· films reported were prepared by means of dip-coating. Kamiya et al. (12) and Ganguli et al (13) converted zirconia into fiber. Sol from Zr alkoxide is usually very unstable, and a stabilizing agent such as glycol or ß-keton is used beforehand (7) (14)."

Jan 1, 2000

By Zhongliang Tian, Yun Cheng, Yexiang Liu, Ming Jia, Yanqing Lai

"A fundamental electrochemical study of Si ions in Na3AlF6-LiF melts and electrolysis using liquid cathodes was conducted. Cyclic voltammograms (CVs) clearly showed the depolarization of silicon deposition on liquid cathode by forming chemical complexes with the liquid solvent metals. Besides, co-deposition of Al and Si is possible when Si ions are insufficient in the molten salt. Based on the electrochemical results, silicon diffusion into liquid cathode is modelled and evolution of Si activity with concentration is deduced by a mathematic approach. Electrochemical study using liquid metals as working electrodes, can be used as an alternative approach for the acquisition of basic data on alloy behavior. Galvanostatic electrolysis showed that liquid cathodes are appropriate to collect the deposited solid silicon and the highest collection efficiency is almost 85%.IntroductionRecent years have witnessed an increasing demand for solar-grade silicon (Si) by the photovoltaic industry [1-4]. The preparation of high-purity metals through electrolysis and electrorefining offer many advantages such as low cost, low-energy consumption, and environment-friendly process, and thus has been widely used worldwide. From the perspective of electrochemistry [5-7], by utilizing the electronegativity difference between the impurities and Si and controlling the relevant process parameters, it is possible in principle to electrodeposit monatomic Si from a Si4+-containing compound melt. Moreover, because the carbon content of the high-purity Si obtained through electrolysis can be effectively controlled and used as a very ideal raw material in the preparation of electronic-grade and solar-grade Si, the preparation of high-purity Si through electrolysis has received widespread attention [8,9]. Monnier et al. [9] used a graphite electrode to obtain high-purity Si (99.9 %-99.99 %) from Si02/Na3AlF6 system through electrolysis; however, because the Si was precipitated in a solid form and showed poor conductivity, the deposition rate was too slow. Olsen et al. [10] obtained high-purity Si films via electrodeposition in K2SiF6/KF-LiF system by selecting electrode materials with high surface quality (such as Ag and graphite). However, in order to ensure the film quality, the deposition current density must be relatively low (10-50 mA/cm2), resulting in a low current efficiency and low deposition rate, which are not conducive to reducing energy consumption and applying to practical use"

Jan 1, 2014

By Dong-dong Liu, Jian-ping Niu, Qi Liu, Shu-sen Cheng

A numerical model was developed to simulate the three-dimensional heat transfer in the belly and lower shaft region of the blast furnace wall consisting of copper steel composite stave, packing and shell. The temperature distribution of copper steel composite stave without the slag layer or refractory lining was investigated and then compared with the copper stave. The results showed that copper steel composite stave can satisfy the requirement of overheatingfree and had an analogous heat transfer behavior as copper stave but more stable cooling intensity. This model had been validated by the good agreement between the computed and measured temperature in the thermal test.

Jan 1, 2015

By R. Padilla, M. C. Ruiz

Arsenic, antimony and bismuth are commonly found in copper concentrates usually as the minerals enargite, stibnite and bismuthinite, respectively. Concentrates having high levels of arsenic and antimony must be pretreated before smelting. Roasting is the preferred method for removing these toxic impurities from concentrates; However, the removal of As, Sb and Bi in oxidizing roasting by volatilization may not be complete due to the slow reaction rates at 500- 700 °C. Oxidizing/volatilization data were obtained from pure mineral mixtures and from arsenic rich copper concentrate. The reaction mechanism for the volatilization of arsenic and antimony were discussed. Near 100% As and over 95% Sb volatilized in the oxidation of a mixture of pure minerals at 700 °C, 1% oxygen, while over 95% As, and 35% Sb volatilized at 600 °C in 1% oxygen atmosphere when using a copper concentrate containing 3.51% As, 0.14% Sb, and 0.01% Bi. Bismuth did not volatilize.

Jan 1, 2015

By Hang Goo Kim

A mathematical analysis based on equilibrium modeling has been developed to describe the distribution behavior of minor elements such as Pb, Zn, Bi, Sb, and As among gas, slag and recovered copper phases during the reduction of copper oxide in slag cleaning with CO gas. The results show that large fractions of the impurities transferred to slag during smelting or converting are recycled to the recovered copper metal. It is also shown that there is a limit to the recovery of copper from slag because iron oxides are also reduced to form a copper-iron alloy at low oxygen potentials. The effects of various operating parameters such as temperature, the activity of FeO, the initial amounts of the elements in the slag and CO content in process gas, on the behavior of these minor elements are discussed. The predicted results were compared with the results of a pilot plant operation in which pulverized coal was used as a reductant. Consistent trends between the two cases were obtained.

Jan 1, 1992

By Batric Pesic

Gold dissolution with bromine was studied by using the rotating disc technique. Geobram TM 3400 was used as a source of bromine. The parameters studied were: rotating speed, Geobrom 3400 concentration, pH, temperature, sulfuric and hydrochloric acid concentration, and the concentration of various cations (copper, iron, zinc, aluminum, manganese, potassium and sodium) and anions (chloride, bromide, sulfate, nitrate, and iodide) According to the Levich plot and activation energy, gold dissolution was controlled by a chemical reaction rate. Copper, iron, and manganese in their highest oxidation states, aluminum, zinc, sodium and potassium did not have any effect on gold dissolution rate. The presence of manganous ion dramatically decreased the gold dissolution rate. Kinetic performance of bromine, in the form of Geobram TM 3400, was compared with performance of cyanide and thiourea.

Jan 1, 1990

A novel process is being developed for metal recovery from waste electrical and electronic equipment involving a leach reactor coupled to an electrochemical reactor. Metals such as Ag, Au, Cu, Pb, Pd, Sn etc. are dissolved from shredded electronic scrap in an acidic aqueous chloride electrolyte by oxidising them with aqueous dissolved chlorine species. In the electrochemical reactor: (i) chlorine is generated at the anode for use as the oxidant in the leach reactor, and, simultaneously, (ii) at the cathode, the dissolved metals are electrodeposited from the leach solution. The extended Butler-Volmer equation was used to provide predictions of the electrode potential dependences of partial current densities and, hence, total current densities, current efficiencies and alloy compositions for acidic aqueous chloride electrolytes containing Ag(I), Au(III), Cu(II), Pb(II), Pd(IV) and Sn(IV) species, together with dissolved chlorine. With judicious choice of kinetic parameters, the predicted total current density ? electrode potential behaviour of such solutions was in good agreement with experimental data for a rotating Pt disc electrode. Reduction of dissolved chlorine at a Pt rotating disc electrode exhibited mass transport controlled behaviour, in agreement with Levich?s equation over the potential range 0.3-0.9 V (SHE). This could form the basis of a linear sensor, possibly using a microelectrode for measurement and control of the dissolved chlorine concentration in the efflux of leach reactors and inlet to electrowinning reactors in the envisaged process.

Jan 1, 2003

By Evgueni Jak

Recent advances in analytical, experimental techniques, and computer-based theoretical modelling of fundamental properties and elemental processes, provide new opportunities to develop the next level of whole-of-reactor pyrometallurgical furnace models. These models have the potential to significantly improve the prediction of, and adding value to, industrial operations. In non-ferrous smelting, the starting point of these models is the development of multicomponent thermodynamic databases for gas-slag-matte-speiss-metal-solids phases supported by systematic experimental research. The whole-of-reactor-models additionally should take into account kinetic processes taking place at micro- and macro- scales, and other key factors. Examples of applications of the latest research tools and modelling approaches to analysis of industrial flash and top submerged lance (TSL) sulphide smelting processes are presented. Different levels of industrial modelling are discussed from elemental local reactions, through general and more detailed whole-of-reactor-models, to plant sections and further to whole plant operation models. Some principles for development of pyrometallurgical reactor models are discussed.

By Robert W. Bartlett

Biooxidation of an ore heap containing only a few percent of sulfide minerals requires insertion of a very large amount of oxygen either by natural air convection, forced air ventilation or gaseous diffusion. While shallow heaps, those with lateral distances much greater than their height, are of great interest for many heaped ore processing operations, natural convection is often ineffective for oxidizing them because of inadequate lateral flow into the heap's interior. Oxygen can diffuse into a shallow heap from its upper, horizontal surface in contact with air. Oxygen diffuses through the air-filled void space within the heap, driven by the oxygen concentration gradient resulting from internal oxygen depletion caused by mineral oxidation. Oxygen diffusion, coupled with the chemical reaction kinetics oxidizing the sulfide minerals, is analyzed for conditions of rapid mineral oxidation kinetics, requiring small mineral grain sizes, and for typical ore heap biooxidation parameters. Practical limits on heap heights are presented for effective biooxidation of the sulfide minerals within times of interest for heap biooxidation of refractory sulfide gold ores, one to three years.

Jan 1, 1995

By Cong Wang, Kexin Jiao, Yongan Zhao, Haibin Zuo, Jianliang Zhang

The carbon composite brick is a new refractory used in blast furnace hearth and bottom. It caused wide attention due to its high thermal conductivity and low erosion by molten iron. In this paper, chemical constituents, SEM-EDS and X-ray diffraction were carried out in order to understand reaction mechanisms. A series of experiments of oxidation resistance characteristics were made. The oxidation mechanisms of carbon composite bricks in the presence of air were analyzed. According to the analysis on many experimental results, the oxidation process of carbon composite bricks under different temperatures were controlled by different mechanisms. In the condition of high temperature, SiO2 as oxidation product hindered the diffusion of O2, and reduced the oxidation loss of graphite in the internal.

Jan 1, 2015

By Christoph Pichler

A special desulphurization slag accrues during the processing of iron ore to steel, which is needed to generate high quality steel. Sulphur removing is done by different technologies, but the most common one is the generation of a high sulphur containing slag by sulphur affine elements. Currently, this desulphurization slag is partly recycled, however, huge amounts are still dumped. To utilize this desulphurization slag for future purposes, a recycling process must be established. Therefore, first characterization of this material started some years ago at the Chair of Nonferrous Metallurgy, Montanuniversität Leoben. Subsequent trials in lab scale size were performed, also some investigations for different treatment steps were evaluated, starting with a parameter study in a hot stage microscope at various gas-atmospheres. Finally, the developed recycling process concept was verified in pilot scale trials to confirm the new recycling technology. Due to the successful treatment process, also a patent was applied.

By G. A. Brooks

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothcrmic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperarure rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (>10 mls) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.

Jan 1, 2003

By G. A. Brooks

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothermic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperature rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (> I 0 mls) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.

Jan 1, 2003

By C. D. Adams, R. T. Tuenge, C. N. King, J. A. Samuels, B. F. Espinoza, R. C. Dye, C. F. Schaus, D. C. Smith, N. M. Peachey

"Recently, doped calcium thiogallate (CaGa2S4) phosphors have been investigated for use in electroluminescent flat panel displays. The current technique used for the deposition of thin film calcium thiogallate is sputtering. Unfortunately, this requires a high temperature annealing process to provide the desired crystallinity of the phosphor. Recent efforts have focused on the possible use of metal-organic chemical vapor deposition (MOCVD) to produce the CaGa2S4 layer. The use of MOCVD provides an attractive alternative to sputtering since it does not require heating above the strain point temperatures of the glass substrates used for the display panels. To accomplish this, the deposition of both Ga2S3 and CaS is investigated as these compounds are intermediate steps in the development of the phosphor deposition. Uniform, crystalline films of both Ga2S3 and CaS were deposited and the process shows promise for successful deposition of the CaGa2S4 phosphor.IntroductionThe lack of a satisfactory blue phosphor having sufficiently high luminances at low power has hampered the development of high resolution flat panel displays. Recently, a new series of blue emitting materials have been investigated for use in thin film electroluminescent (TFEL) devices. l ,2,3 These phosphors are based on a series of alkaline earth thiogallate host materials of the form MGa2S4:RE where M can be either calcium, strontium, zinc, or barium and RE is a rare earth ion. A full-color VGA TFEL panel using CaGa2S4:Ce as the blue phosphor has recently been fabricated and tested. l This FPD provided a luminance of 10 cdlm2 at 60 Hz. The enhanced blue in this display allowed its color capabilities to approach those of the conventional CRT.The method of depositing the phosphor onto the display panels in these test devices has been sputtering. Unfortunately the phosphor as deposited does not possess the crystalline properties required for optimum luminance. The crystalline structure is achieved by subsequent annealing of the deposited material. Although this post deposition anneal provides the desired crystal structure, it occurs above the strain point temperature of ordinary glass. Consequently, the implementation of these phosphors requires the use of glasses capable of withstanding high temperatures, adding to the cost of the final display unit."

Jan 1, 1994

By Elli Miettinen

In Copper Flash Smelting operation disturbances may lead into dust build-up in the gas train and off-gas handling system causing reduced heat recovery efficiency and process availability. Flue dust of a Copper Flash Smelting process heat recovery boiler has been characterized and its thermal conductivity and diffusivity have been determined. Dust accretions consist of several layers possessing varying particle sizes, densities, and thermal properties, with the binding phase usually being sulphate. All the dusts can be regarded as effective thermal insulators with thermal conductivity values of less than 2 W/mK and thermal diffusivity values of less than 0.005 cm2/s. Porosity can be regarded as a fairly good indicator of the thermal transport efficiency of these types of materials, but the material microstructure must also be considered. The results can be used in the dimensioning of metallurgical heat recovery boilers and they also provide accurate input data for process models.

Jan 1, 2009

By Sylvain Gouttebroze, Mohammed M'Hamdi

In a previous work, a small scale Bridgman furnace has been used to study silicon bi-grain crystallization at different cooling rate. This work expands the analysis by studying the mechanical interaction between the crucible and ingot during the solidification and cooling. The thermal model is based on a 2D-axisymetric heat-transfer model. The flux histories are then transferred to the ingot-crucible 3D-model. Anisotropic Elastic and Crystal Plasticity model are used to model the silicon deformation. Four different assumptions are applied to model the mechanical contact crucible-ingot and three grain misorientations are considered. The results show the strong impact of the alumina crucible contraction on the stresses and deformations in the silicon ingot.

Jan 1, 2015

By Xiao Yang

Calcium oxide is one of the major fluxing agents used for steel refining. Because unreacted CaO remains in slag in most cases, discharged slag is difficult to be recycled smoothly. With the growth of environmental concerns, improving utilization efficiency of CaO is required to reduce the amount of discharged slag and energy consumption. The authors have reported a resource and energy-saving process by using multi-phase flux for dephosphorization. Reaction behavior of phosphorus in multi-phase CaO–FeOX–SiO2–P2O5 flux system was investigated. Formation mechanism of P2O5-rich phases was clarified at the interface between solid CaO or 2CaO, SiO2 and molten CaO–FeOx–SiO2–P2O5 slag. Phase relationship and thermodynamic properties of 2CaO, SiO2-3CaO, P2O5 solid solution were observed to confirm the condensation of P2O5 in solid phase. Based on these results, reduction of CaO consumption, discharged slag curtailment, and energy-saving effects in the novel refining process by using multi-phase flux were discussed.