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By Wilson Pascheto

This paper presents results of investigations performed as part of a Root-Cause-Failure-Analysis (RCFA) of a DC smelting furnace that was brick lined with MgO-based refractories. An unusual continuous contraction of the furnace hearth was identified during operation. Cracks in the refractories were envisaged after a major shutdown of the furnace. To determine the mechanism and causes of the unusual contraction behaviour of the furnace hearth, refractory samples were taken from the furnace at different locations and subjected to different analysis including Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDX), QEMSCAN and Electron Probe Micro Analysis (EPMA). Creep testing of refractories under different loads (ASTM C832) was also employed to evaluate the mechanical integrity of the used bricks in comparison with the new ones. Results of the various characterisation analyses revealed that there was an interaction between refractory bricks and molten material during furnace operation, which resulted in reduced creep resistance of the MgO-based refractories. This was verified by comparing creep performance of the used brick samples and new brick samples at different temperatures and applied stresses.

By Xuyang Liu, Xuewei Lv, Chenguang Bai, Meilong Hu

"The electro-deoxidation process for ilmenite concentrate in molten salt was studied by cyclic voltammetry and AC impedance spectroscopy. The results from cyclic voltammetry are consistent with those of AC impedance spectroscopy. The results showed that the electro-deoxidation process for ilmenite concentrate consists of two steps. In the first step, Fe is reduced from the ilmenite concentrate. The second reaction is the decomposition of TiCh. CaTiCh is an intermediate product. At low voltage, the electrochemical reaction is the main step. With the increasing potential, the diffusion of ion is the main rate controlling step for the electro-deoxidation of FeTiO3.IntroductionTitania and titanium-rich products are mainly prepared from ilmenite concentrates (FeTi03), which contain about 40%-60% T1O2 after ore dressing and other physical or chemical processes [1]. At present, the main methods to prepare titania are the sulfuric acid process and the chloride process, but the sulfuric acid process consumes a large amount of sulfuric acid and the materials requirements for the chloride process are strict [2], Since the Electro-Deoxidization in Molten Salt (FFC) method was put forward in 2000, many researchers have successfully extracted the metal and alloys by this method, such as Ti, Cr, Tb, Si, Al-Si, TiV, FeTi, etc. [3-7], FeTi alloy is a typical hydrogen storage material, and because of its favorable properties, the preparation of FeTi alloy has become a hot research topic [7-9]. However, the mechanism of electro-deoxidization has not been studied thoroughly [10-11]. Therefore, in this study, the electro-deoxidation process for titanium concentrate was investigated by electrochemical methods, and the study makes a contribution to improving the current efficiency of the electrolysis."

Jan 1, 2012

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 Javier Antoñanzas, Susana Caballero, Eduardo Fernández, Jorge Aragón, Juan Carlos Múgica, Lourdes Yurramendi

Air Pollution Control (APC) residues treatment by plasma was studied as a technology for vitrification. During the project a protocol to verify the plasma technology was developed and afterwards applied to a specific case study: the APC residues from Municipal Solid Waste Incinerators (MSWI). Different operational conditions were tested and the vitrified products obtained were analyzed using standardized leaching tests in order to evaluate their new properties concerning safety storage. Two leaching tests were used for the evaluation, the European EN 12457-4 compliance test for leaching of granular waste materials and the French XP X 31-211 test for the determination of the leachability of a solid waste material initially massive or generated by a solidification process. Finally, conclusions about the environmental performances of the technology were obtained.

Jan 1, 2008

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 Carla Lupi

Zinc electrowinning from sulfate solutions is the traditional industrial method to produce SHG zinc. Over the past few years several efforts have been done to improve process efficiency in order to reach high productivity with low energy requirement. The latter aim can be pursued both by means of a hard purification of the electrolyte and reducing the anodic voltage. This work is a comparative study of the results obtained in several previous researches on zinc electrowinning from both sulfate and chloride solutions. Zinc electrowinning tests on industrial sulfate solution have been carried out by using Pb alloy anodes and by adding organic depolarizers such as ethanol, acetic acid or ethylene glycol. Experiments on chloride solutions, obtained by purification of zinc exhausted electrolyte, have been performed by using DSA anodes and by testing the effect of additives such as TEACI and TBAC\. Comparing the best results obtained with the two methods it can be highlighted that a high quality zinc is electrowon in both cases with comparable energy requirements.

Jan 1, 2000

By Marco Antônio Siqueira Rodrigues

The possibilities for treating rinse waters fiom chromating bath by electrodialysis are discussed together with the possibilities of optimizing the treatment process for waste reduction and reuse of water and chemical products. An industrial effluent with 4600 ppm of Cr(VI), besides other metallic contamination, was used as work solution. This solution has been recirculated on an electrodialysis cell of three compartments, using exchange membranes Selemiom AMT and CMT. A migration of dichromate ions into the anodic compartment was obtained, so that an extraction of circa 99.9 % of Cr(VI) present on the solution was observed, resulting in water with a Cr(V[) concentration of 4 rnd. These results show that electrodialysis can be used to treat these effluents, and this water could be reused as rinse water. The solution of the anodic compartment, consisting at the beginning of the experiment of H2S04, 0.1 N, reached 7200 mg/l of Cr(VI). This concentrate could be reused on the chromating bath itself.

Jan 1, 1999

By Jay S. Gunasekera

Metal parts are traditionally processed by either filly-liquid (e.g., casting) or filly-solid (e.g., forging) state. Semi-solid metal forming incorporates elements of both casting and forging. In 1991, Gunasekera(5) developed a model illustrating the influence of flow stress by the liquid fraction. The result fits Kiuchi's (1979)(7) experimental data quite well. This model assumed the liquid part is surrounded by solid as small pockets inside the material, which is opposite to the real practical situation. Since the melting usually first happens at the grain boundary, it is better to treat the semi-solid material as small metal crystal surrounded by liquid.

Jan 1, 1997

By C. Gasparrini

Mineralogy may be applied to the selection of appropriate separation techniques, as well as to assist in the evaluation of problems causing loss of metals and other economically important elements during plant processing. Mineralogic studies may thus help develop techniques to optimize metal recoveries. The present paper describes how such factors as the minerals in which the elements of interest are concentrated, their chemistry, the chemistry of the associated minerals, grain size and textural associations with other minerals in the ore, may affect decisions on separation techniques for the recovery of economic elements. A number of case studies are described in which the mineralogical observation of ore samples has revealed the cause of problems experienced in the extraction of select precious and base metals, or has been decisive in the choice of appropriate techniques for recovery.

Jan 1, 1981

By G. G. Barbante

Copper anode slimes are a valuable source of the precious metals, and selenium and tellurium. They are mineralogically complex and this has led to a great variety of process flowsheets for treating them. The traditional pyrometallurgical method utilises oxidation in a reverberatory furnace, but has numerous shortcomings. Recently deep-bath intensive smelting methods have been developed for use in the larger refineries. Despite these process advances, the thermodynamics of the reactions involved remains poorly understood. An initial description of the thermodynamics of slimes smelting is presented, but is severely limited by a lack of basic data. It is shown that slimes smelting is superficially similar to copper converting, but has many unique features. More basic thermodynamic data on selenium-based systems are needed before the process model presented can be further refined, and work in this direction has already commenced.

Jan 1, 1994

By Caisa Samuelsson, Taishi Matsushita, Hannes Holmgren, Sina Mostaghel

"Rönnskär Smelter of Boliden Mineral AB, Sweden, is a large end-processor of secondary raw materials and waste, including electronic scrap. Electronic scrap may introduce various impurities to the smelter's flow-sheet, among which alumina is a common and significant one. This article summarizes the results of an ongoing research at Luleä University of Technology, Sweden, to study the influences of alumina on different properties of slag from the zinc fuming process at Rönnskär smelter. A combination of different experimental techniques and thermodynamic calculations have been used to investigate properties such as density, surface tension, effective thermal diffusivity, viscosity, and melting/leaching behaviors. Results show that the addition of alumina to this slag increases the degree of polymerization of the melt, and physical properties vary correspondingly. Mineralogy of the semi-rapidly solidified samples is also changed due to alumina addition. A correlation between mineralogy and leaching behavior can be observed.IntroductionBoliden's Rönnskär Smelter is a base- and precious-metals producer located in north of Sweden. Its main products are copper, zinc clinker, lead, gold, and silver. Sulphuric acid, liquid sulphuric dioxide and iron sand (granulated slag) are some of its main by-products. In order to optimize the overall outcome of the process, different refining units are integrated in the smelter's flow-sheet (Figure 1). Copper concentrates and fluxing materials (mainly silica sand) are charged to the process. The produced matte is sent to the converter and the generated slag is charged to the fuming furnace, where it is treated by reducing gases to produce zinc clinker. The converter's slag is charged to the electric furnace, while the fumed slag is tapped into the settling furnace for further cleaning, where matte, slag and speiss (residual metals) are separated. The matte from the settling furnace is also sent to the converters; its speiss is sold to external customers; and its slag is water granulated and sold as construction material, which is known as iron sand."

Jan 1, 2012

By Anjan Kumari, B. K. Soni, Manis Kumar Jha, A. Vidyadhar, Vinod Kumar

"In the present paper, recovery of valuable metals from the poly-cracked ash obtained by pyrolysis of discarded PCBs has been studied following physical beneficiation and a hydrometallurgical process alternate to smelting. The ash is subjected to comminution for the separation of metallic components from non-metallic fractions by scrubbing, tabling and froth flotation which enriched the metal in the concentrate -97% which was further screened to separate high and low metal concentrate. The finer fraction containing -12% metallic value was leached in acidic solution. Almost all (Cu, Pb, Fe, etc) were leached in 4M HN03 at 90°C in 75 min at a pulp density 100 g/L. The characterization of both ash and residues were made by XRD, EPMA, EDS, etc. to validate the experimental results. The metals from the leach liquor could be recovered/separated using solvent extraction techniques which can further be processed to get pure metal salts/ sheets.IntroductionPrinted circuit boards (PCBs) are an essential component of electrical and electronic equipments (EEEs) as it plays an important role during operation of these devices. The world market of PCBs has reached nearly $60 billion in 2012, with 1.7 percent real growth over 2011 [1]. The diverse technology-driven global market is expected to grow at an average annual rate of 5% by 2014 [2]. The waste EEEs are generated due to replacement of obsolete equipments with modem ones and thus their demand is also increasing rapidly [3]. The discarded e-wastes are being piled up as landfills which affect the environment and cause health threats to living organisms, if not disposed of properly. These e-wastes contain metals some of which are precious, few are hazardous and others as valuable."

Jan 1, 2014

By Valery Kaplan

Sulfur emission in the form of SO2 in flue gases is one of the most serious atmospheric pollutants associated with coal combustion and non-ferrous metals production. The carbonate eutectic method for removing SO2 from flue gases at 723–923 K was initially proposed in the 1970s but despite its great efficiency (SO2 concentration in the flue gas after purification reached 0.003 volume %), it could not be implemented by industry due to the complexity of the carbonate melt regeneration stage. Earlier we proposed a method suited to coal-firing power stations where the melt was regenerated using CO as a reducing agent. However, most metallurgical plants do not use coal and therefore lack a large source of CO. Here we propose a method for removing sulfur from the carbonate eutectic melt by purging it with natural gas or a natural gas/air mixture, which are available in the vast majority of metallurgical plants. This reaction leads to the reduction of sulfate to H2S gas that leaves the melt. The experiments we conducted show that nearly complete sulfur removal from the melt is possible at 823 K and that the reaction rate is sufficiently high for a large scale process. One can foresee that this carbonate melt-based SO2 removal technique may become a practical and economically attractive method for limiting sulfur emission to the atmosphere from non-ferrous metallurgical processing plants.

By Hans Jürgen Maier, Hans-Bernward Besserer, Gregory Gerstein, Florian Nürnberger

The formation and development of voids in both the single-phase ferritic steel DC04 and the dual-phase ferritic-martensitic steel DP600 are discussed. Various mechanisms and kinetics of void formation are considered regarding the influence of dislocation glide, precipitates and other parameters. Different characteristic locations in the microstructure are investigated at which strain concentrations during plastic deformation can occur and cause the formation of voids and microcracks. For the specimen preparation ion slope cutting is applied. Voids and cracks revealing ductile damage are analyzed by Scanning Electron Microscopy (SEM). Stress concentrations in consequence of plastic deformation could be shown by extinction contours on images recorded by Transmission Electron Microscopy (TEM).

Jan 1, 2015

By Jafar Safarian, Merete Tangstad, Leiv Kolbeinsen

"Silicon and its binary alloys have several applications in metallurgical, chemical, photovoltaic and semiconductor industries. Silicon goes to its liquid state within its production, refining and when it is alloyed with other elements. Therefore, the characterization of silicon melts thermodynamics is important and useful. The liquidus and activities in several silicon binary systems have been recently calculated by the application of two liquidus constants, which were established using the experimentally determined liquidus data. In the present study, the thermodynamic properties of six silicon binary melts, which are simple eutectics, are calculated by analytical approaches. In this case, the changes in the partial and integral Gibbs free energies and enthalpies of mixing are calculated and compared with the experimental data in literature. The enthalpies are calculated by two methods and the calculation results are compared to the data from the literature. It is shown that thermodynamic properties of silicon binary melts can be accurately predicted without the use of complicated thermodynamic software.IntroductionSilicon and its alloys have several industrial applications. Silicon is used for making aluminium-silicon alloys to produce cast parts, mainly for automotive industry. Silicon in the form of ferro-silicon is used to deoxidize and alloy steel and cast iron. The photovoltaic (PV) industry has had a rapid growth in the recent years and silicon is the dominant material used for the fabrication of solar cells. Silicon is primarily produced through carbothermic reduction of quartz in electric arc furnaces and the produced metallurgical grade silicon (MG-Si) contains around 1 wt% impurities. It is further refined to produce solar grade silicon (SoG-Si) with above 99.9999 wt% Si to fulfil the chemical requirement for PV application. Since molten silicon is processed all along the metallurgical route, obtaining fundamental thermodynamics knowledge about silicon melts is valuable for the related industries."

Jan 1, 2012

By Ma Lijuan, Zhang Yubing, Wang Bo, Sun Huilan

The effect of lime ratio on phase composition and alumina leaching property of MgO-contained calcium aluminate clinker were investigated by analytical reagent, the XRD analysis of its mechanism was discussed. The results showed that: when the sintering temperature was 1350 ℃, C/A was 1.4, A/S was 1.3 and the content of MgO was 4%, the increase of the C/A promoted the formation of C12A7 and restrained the formation of Q-phase. The alumina-leaching ratio of the clinker (A/S was 1.3) was increased from 74.33% to 91.34% when the content of CaO was 5.21%.

Jan 1, 2015

By Levente Becze

The zinc bottom dross is obtained as a by-product from hot dip galvanizing operations and contains at least 92 % zinc, which is recycled mainly by pyrometallurgical processes. The overall costs of such a treatment, however, are often relatively high, and the very strict environmental protection regulations might also cause additional difficulties for the high temperature procedures in the future. Therefore, a novel hydro-electrometallurgical process has been developed in our laboratory, by which one can reclaim zinc of high purity, while attempting to achieve low energy consumption and making allowances for all the environmental restrictions. This aqueous processing technique, based on electrolytic refining in a cell equipped with anion-exchange membrane to separate the anode and cathode compartments, allows the indirect purification of the anolyte. Zinc is dissolved from the anode along with some of the impurity elements, while the intermetallic compounds (Fe-Zn, Fe-AI- Zn) are accumulated in the anode slime.

Jan 1, 2003

By Zhihe Dou, Yan Li, Qiuyue Zhao, Guozhi Lv, Yan Liu, Hongliang Zhao

"Abstract: How to reduce carbon dioxide emissions has become a vexing problem, meanwhile, there exist high energy consumption and low efficiency problems in the existing CO2 capture and storage technologies. For CO2 comprehensive Utilization, this paper researches a new technology of absorbing the CO2 emission with high alkaline calcium or high alkaline wastewater sludge mineralization of calcium and invent a core device for multi-level jet carbonation. The industrial test has been carried out in China Xinyu slag Engineering Co., Ltd. The wastewater flow is 150m3/h in the pilot scale. The prepared calcium carbonate has a whiteness greater than 90%, particle size less than 150nm. The mineralization of aluminum exhaust with waste carbide indicates that the CO2 absorption rate is greater than 99.0%, CO2 concentration in the exhaust gas is lower than 0.08%, the purity of mineralized calcium carbonate is greater than 99.0% and particle size is less than 100 nm.InstructionAccording to the statistic data from IEA (2009), the carbon dioxide discharge from fossil fuel consumption in China has exceeded it in the US by the year of 2007, China, has become the largest emitter of carbon dioxide all over the world. Meanwhile, the economic scale is still on an increasing trend in the next 50-100 years, leading to a continuous increment in carbon dioxide discharge. According to the international energy agency forecasts, the energy-relative CO2 discharge in China will rise to 11,615 million tons, 91.3% higher than it in 2007. In the year of 2012, the CO2 gross discharge has reached 10,000 million tons, obviously higher than the predicted value. It is a tremendous task to reduce the emission. Non-ferrous metals industry is one of the largest emitters of carbon dioxide among the industrial circle, the whole industry might discharge a huge amount of carbon dioxide (over 600 million tons), in which the electrolytic aluminum industry is the largest energy consuming industry and CO2 emitter. At present, the CO2 discharge has focused by the whole world due to the environmental problems it causes; meanwhile, supplement of new carbon source is needed due to the exhausting oil and coal resources, so that various countries in the world are attaching importance of the recycle and purification of CO2. Many countries are studying on the cyclic utilization of carbon dioxide. Gas CO2 is mainly applied in chemical, pharmaceutical raw materials, beverage filling agent, refrigerant, inert medium, solvents, pressure source, the welding protective gas, antioxidant and fire extinguishing agent, etc. Solid CO2 is mainly applied in penicillin production, fish, cream, ice cream and other food storage and transportation at low temperature, etc. nowadays, such methods as absorption method, membrane separation, adsorption, etc. are widely used to recycle CO2, with such problems as high investment cost and technical constraints etc."

Jan 1, 2014

By John A. Mavrogenes

The Texaco gasification system developed at the Monte Bello pilot plant efficiently bums petroleum-coke thereby producing syn-gas and electricity. This system produces more electricity than conventional burners, yet the only by-products are pharmaceutical grade sulfur and V -rich slag. Vanadium is known to exist in multiple valence states in compounds which possess a wide range of melting points and physical properties. Consequently, it becomes important to carefully regulate oxygen fugacity throughout the system in order to control vanadium valence state. Vanadium phase equilibria is presently poorly understood, in large part because of the multiple oxidation states of vanadium (-I, 0, +2, +3, +4, and +5) and the difficulty of unequivocally identifying the valence state(s) in many compounds. The operation of these gasifiers at approximately 1400°C is well above the melting point of V20S but considerably below the melting temperature of V02 and V 203. If J02 can be regulated to keep the burner within the V 205 field, slag material would more likely remain molten and more easily flow out of the bottom of the burner. In pure V oxides. the oxidation state is readily determined by microprobe analysis. where V20S (V+5) is 56% V, V02 (V+4) is 61.4% V, and V203 (V+3) is 68% V. However, V valence in multi-element phases (especially phases containing other elements of variable valence) cannot be resolved by microprobe analysis alone. Petroleum-coke gasification slags collected from within the gasifier under different oxidation conditions were studied by electron microprobe analysis (EMPA). X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Raman spectrometry in conjunction with microprobe analysis was found to resolve the valence of vanadium in the phases of these slags. Raman spectra collected from homogeneous single phase V-oxide standards in vacuum at low temperatures (-150°C) yielded peaks characteristic to each valence state. Gasifier slag samples are, however, much more complicated. Oxidized samples contain: fine grained (Ca. Mg, Fe. V) oxide matrix of variable composition, (Fe. V, Ni) spinel. (Fe, AI, V, Ni, Mg) spinel, V205laths, AI-Si glass blebs and Ni sulfides. Reduced samples contain: crystalline Ca-siIicate matrix, subhedral to euhedral (V, Fe, Mg, AI) spinel, subhedral V02, Fe and Fe-Ni sulfides, Fe-Ni alloys, and complex Ca-oxide matrix. The different spinel assemblages, the characteristic V-oxides and the distinctly different character of the matrices makes the oxidized and reduced slags readily discernible.

Jan 1, 1995

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