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By Krzyszof Borowiec

With the aim of determining the thermodynamic conditions for sulfation of impurity elements, in particular magnesium, in titaniferous slags the equilibrium gas composition for the sulfation reaction: MO + so2 + 1/2 02 = MS04 has been studied by an EMF technique with a solid zro2 + Cao electrolyte. Here M denotes the impurity elements: Mg, Ca and Mn, and the following _oxide systems have been studied: Ti02-MgO-Fe2 o 3 , Ti02-MnO-Mn2 o 3 , and Ti02 -CaO-Si02 , all in the . temperature range 700-1000ºc. Reproducible EMF values were obtained by adding small amounts of -Na2so4 to the oxide-sulfate mixture. From the observed results the Gibbs energy of formation of the phases Mg 2Ti04 , MgTi03 , MgTi 2o 5 , MnTi03 , CaTi03 , and CaTiSio5 , as well as the activity of MgTi05 in the solid solution with Fe2Ti05 have been calculated. The results show that, from a thermodynamic viewpoint, sulfation of these impurities in titaniferous stags i:s favorable- at around and below 800ºC.

Jan 1, 1985

By William C. Spindler

Five industrial installations of large lead-acid battery energy storage systems in operation in the United States, West Germany and the 'Republic of South Africa will be described. One example is for a deep mine shaft in which air ventilation and personnel evacuation require the highest reliability for emergency power. The battery system is designed for additional cost-effective benefits of peak load lopping and reactive power control. Commercially available lead-acid batteries of the following types are in use1 traction, truck, submarine, high power, and gel. Electrode grids of both the calcium and antimony alloy types are used. Applications include deep and shallow cycling as well as float and intermittent use. The advantages of sealed lead-acid batteries in UPS (uninterruptible power source) systems are well established throughout the world, and such system suppliers could readily develop markets for industrial emergency and peak power lead-acid storage battery installations.

Jan 1, 1990

By W. K. Connor, O&apos

The U.S. Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory (INEL), conducted over 30 hours of melting tests to vitrify simulated low-level radioactive wastes from the INEL Radioactive Waste Management Complex (RWMC). Five separate waste compositions were investigated, each consisting of noncontarninated soil from the RWMC and surrogate materials used to simulate the actual buried wastes. The RWMC soil and five waste compositions were melted in a 50-lb, single-phase electric arc furnace with a water-cooled shell. These tests were conducted to determine melting parameters in preparation for a large-scale melting campaign to be conducted in the Bureau's 1-metric ton (mt), water-cooled-wall, 3-phase electric arc fumace. Bulk chemical composition was determined for each of the feed materials and for the slag, metal, fume solids, and offgas furnace products, and distributions were calculated for the key elements. The material balance for the furnace operation indicates that from 63 to 84 pct of the feed reported to the slag. Cerium, used as the surrogate for the radionuclides in the wastes, demonstrated an extremely strong affinity for the slag product. Although slag temperatures as low as 1250° C were recorded when melting the RWMC soil, temperatures in excess of 1600° C were necessary to achieve the fluidity required for a successful slag tap.

Jan 1, 1994

By Francis C. Furman

Microscopic evidence indicates that the high sinterability of certain commercial dolomites is tied to specific dolomite textural characteristics. This study encompasses detailed characterization of the unprocessed dolomite and sintering doloma results. The chemical and mineralogical compositions, insoluble residue, chemistry homogeneity, crystal size, primary carbonate texture, secondary dolomite texture, deformation structure, porosity type, porosity, and density of the raw dolomite were observed. These characteristics are compared with sintering trials of <74um powder-compacts samples in which holding times were varied. The evolution of the dolomite characteristics are reviewed and related to the final sintered doloma characteristics. The critical characteristics of a single-stage sintering brick dolomite are the following: 1) primary oolitic texture, 2) dolomite purity, 3) dolomite stoichiometry 4) minimal impurities, less than 1 weight {%} Fe2O3 Al2O3 and SiO2, 5) chemical homogeneity, 6) high density, 7) very low porosity, S) very coarse homogeneous crystallinity, 9) nonplanar dolomite texture, 10) abundant strain related slip microdeformation structures, 11) minimal subsequent alteration. Even with grinding to <74um the nonplanar dolomite texture and slip deformation still have a major effect on doloma sintered density. The three newly identified characteristics of single-stage sintered refractory brick dolomite are their primary oolitic texture, secondary nonplanar texture and abundance of stress related microdeformation structures. The primary oolitic texture reflects a homogeneous pure carbonate with respect to chemistry and crystal size secondary nonplanar texture produces crystals with large surface area to volume ratio. Stress related slip deformation moves CO, groups in to the same site of another CO, group but different orientation which is very unstable. All of these characteristics may facilitate the formation of higher density dolorna sinters.

Jan 1, 1995

By Yong Hack Lee

Nonferrous smelting processes have been through a rapid transformation since the beginning of 1980. The copper smelting technology has changed from the conventional Blast Furnace process to the Flash Smelting and MIB process. In the field of lead smelting, the technology has changed from the Blast Furnace Smelting to the Direct Smelting such as QSL and KIVCET. In 1992, Onsan Refinery successfully commissioned Direct Smelting QSL technology for lead. The QSL could produce more than 160,000 ton per year of lead bullion from lead concentrate and various residues. Moreover, since the year 2000, the TSL (Top Submerged Lance) Technology utilizing the same Direct Smelting process has been successfully commissioned to treat lead concentrate as well as lead sulfate residue produced from a hydrometallurgical zinc plant. This paper presents and compares the energy flows of lead smelting processes such as a conventional process and the Direct Smelting Processes plotted on the Pb-O-S phase diagram. The oxygen potential diagram suggests how to control the oxygen potential in the furnace. Also, it describes the recent operational experience in the TSL plant of Onsan Refinery with necessary mass balance of key elements.

Jan 1, 2003

By A. Mezei

Samples of cobalt and bismuth concentrates produced from the NICO deposit in Northwest Territories were subjected to a comprehensive metallurgical testwork consisting of: pressure oxidation, ferric chloride leach and carbon in leach, to recover the cobalt, bismuth and gold, respectively. A specific testwork program was designed to allow for the optimization of process parameters under multiple restrictive criteria. The overall objective was to establish leaching sequences that could produce acceptable recoveries while generating environmentally disposable residues as well as solutions suitable for further processing. The recoveries for the leaching stage, under the optimum conditions, were 97% for cobalt and 95% for gold, in the case of the cobalt concentrate. The bismuth concentrate produced recoveries of 99% for bismuth, 99% for cobalt and 97% for gold, respectively

Jan 1, 1999

By Michael Sheedy

Sulfuric acid is widely used as an electrolyte for the electrorefming and electrowinning or metals. Impurities in this electrolyte are controlled by continuously bleeding solution from the tank house. In addition to the contaminant these bleed streams contain high levels of sulfuric acid and the metal being recovered. Subsequent treatment of these bleed streams often requires neutralization which generates large volumes of solid waste. Absorption resin technology employing a novel ion exchange technique known as Recoflo® allows the separation of the mineral acid from dissolved metal salts. The recovered acid is suitable for recycle back to the electrolyte circuit. The metal salt and other contaminants leave the process free .of the sulfuric acid. In this process, known commercially as the APU®, ion exchange resin is used to sorb sulfuric acid while excluding the metal salts. The purified acid is then removed by washing the resin with water. The process has been extensively used for the recovery of waste pickling acids in the steel industry and anodizing solutions in the aluminum industry. In the mining and metallurgical industries the process has been successfully evaluated for the separation of excess sulfuric acid from copper electrolytes, the removal of magnesium and manganese contaminants from zinc electrolytes, and nickel and copper from copper electrolytes. A full scale installation on a copper refinery bleed stream at Palconbridge's Kidd Creek plant in Timmins, Ontario has now been operating successfully for more than 1 year while pilot field trials have been successfully completed on other applications.

Jan 1, 1997

By Phillip A. Armstrong, Charles A. Lewinsohn, John H. Gordon

"This paper describes the opportunity offered by employing systems based on mixed conductive ceramics, in particular, ceramics conductive to oxygen ions and electrons, in reducing CO2 emissions from metallurgical production. Membranes based on these mixed conducting properties enable commercial viability of several attractive metallurgical processes. One of these processes utilizes modular, ceramic-membrane structures for the generation of pure oxygen, in tonnage quantity. The membrane-based systems offer significant capital savings and operating efficiencies in various metallurgical processes. The current status of this technology is summarized below.IntroductionCryogenic oxygen supply technology is currently the state-of-the-art for applications that require large quantities of oxygen (hundreds to thousands of tons per day). Cryogenic technology, however, requires substantial energy inputs and, hence, adds significant costs and emissions to processes. Furthermore, cryogenic oxygen supply technology is mature and there is relatively little potential for substantial capital cost reduction or efficiency improvement in coming decades. Non-cryogenic technologies offer a means to reduce the environmental footprint and cost of the oxygen supply facility in various applications.Ion Transport membranesCommercially available non-cryogenic air separation technologies, such as adsorption-based and polymeric membrane-based methods, do not afford the economies of scale that the cryogenic distillation enjoys. Therefore, industrial gas industry researchers began searching for alternatives to the relatively inactive and unselective polymeric membrane materials available. In the late 1980’s, Air Products began developing a new class of highly selective membrane materials with exceptionally high activity for oxygen transport. The materials constitute a class of oxide ceramics, and conduct both oxygen (as oxygen ions) and electrons in the same membrane, separating oxygen from air electrochemically. Numerous detailed process economics studies have shown that, based on these ion-transport membranes (ITM’s), the cost of oxygen can be reduced by approximately one-third relative to that obtained from state-of-the-art cryogenic oxygen supply technology, through a combination of capital cost savings and efficiency improvements. [1,2,3]"

Jan 1, 2008

By Gang Qi

The solubility of nitrogen in pure molybdenum was measured over the temperature range 2173 to 2473 K and up to one atmosphere (101 kPa) of nitrogen gas pressure. Both thermochemical and kinetic aspects of this phenomenon were considered in this study. The solution of nitrogen in molybdenum may be expressed by the reaction 1/2N2(g) = {N} (Mo,s), for which the standard Gibbs energy is given by the expression {A}G° = 78,500 + 27.36T Joules/g atom N. The formation of molybdenum nitrides, specifically Mo2N, was considered. Attention was also focused on the mechanism of nitrogen solution in molybdenum. Estimates of the diffusivity of nitrogen atoms in solid molybdenum were derived from the kinetic data.

Jan 1, 1991

By Geoffrey A. Brooks, M Akbar Rhamdhani, Md Saiful Islam

A novel electrically-enhanced metal purification using slag has been developed. This was achieved by applying DC potential between liquid metal and slag phases. The concept was demonstrated through small-scale experiments at temperatures of 1500-1600oC for the removal of boron from Si-B melt using CaO-SiO2-16wt%Al2O3. Silicon (containing B) and slag were reacted in an alumina crucible in a resistance tube furnace. A circuit was produced by immersing graphite rods into the silicon bath and the slag layer. Electrical potential differences of up to 3.5 V were applied during the reactions. The reaction rates, the opencircuit voltages and short-circuit currents (in the case when the potential was applied) were then measured and determined for various slag to silicon ratio. It has been shown from this study that both the apparent rate and the boron partition ratio were increased by a factor of approximately 1.6.

Jan 1, 2014

By S. S. Chabot, S. E. James

A recent survey of CEOs from major steel companies worldwide revealed the importance of recycling zinc units from EAF dust, mill scale, blast furnace dust, and other zinc containing streams in their plants. Many processes were developed and installed in response to this challenge. The most successful approach involves the production of a crude zinc oxide and selling it to primary zinc producers to recover the metal value. The problem with this process is the high concentration of halides in the crude oxide. This type of material cannot be processed directly in an electrolytic zinc plant because of corrosion problems it will cause in electrolysis. In 1999, BRZ installed a zinc oxide receiving and washing plant to minimize the impact of halides to its circuit. A description of the washing plant and initial operating results are included.

Jan 1, 2000

By C. A. Nogueira, F. Margarido

"A research work has being carried out annmg at evaluating the possibility of treating simultaneously several electrochemical systems of spent batteries using the same process, in order to overcome the high costs and difficulties of selective collection and sorting. Zn-Mn02 systems, representing more than 75% of portable battery market, shall be treated in dedicated processes. The treatment assessment using a single hydrometallurgical process of the other major systems (NiCd, NiMH and Li-ion), having Ni and Co as main metals, was the aim of the research work here reported. Sulfuric acid leaching was demonstrated to be adequate for dissolving more than 90% of the metals of interest contained in batteries. The subsequent separation of metals by solvent extraction, using organophosphorous extractants like DEHPA and Cyanex 272, allowed the production of pure solutions of rare earths, cadmium/manganese, cobalt, nickel and lithium, enabling their further recovering.IntroductionRecycling is the best approach for end-of-life management of spent batteries mainly by environmental reasons but also motivated by resources conservation and, in some cases, by economic profits. Most relevant electrochemical systems of portable cells are Zn-Mn02 (ZMB, alkaline and saline), nickel-cadmium (NiCd), nickel-metal hydride (NiMH) and lithium-ion (LIB). These batteries are collected, sorted and usually treated separately, applying for pyrometallurgical or hydrometallurgical technologies, the former being the most common.Several processes have been developed and some of them industrially applied, as described in some available review papers [l, 2]. In Europe for ZMB systems the oldest processes are Batrec [3] and Citron [4]. Although having differences in details, both are based on pyrometallurgical recovery of zinc by distillation, in metallic or oxide forms, being manganese retained in the slag together with iron. Hydrometallurgical alternatives are also available, like Zincex [5] and Recupyl [ 6] processes, both using sulfuric acid solutions as leachant. The application of the existing technologies to battery recycling, instead of using dedicated processes, is other alternative already tested, being the Waeltz furnace or the Imperial Smelting some examples."

Jan 1, 2012

By I. D. Reznik

The flowsheets of converter matte production from sulphide copper - nickel and oxide nickel ores on Severonickel and Yuzhuralnickel integrated ,;corks are given. The cobalt behaviour in electrosmelting and autogenous ore smelting, converting and converter slag cleaning is observed. A list of acticles published in the 80 th is given.

Jan 1, 1993

By S. A. Shuey

The present industrial practice used to separate aqueous cobalt from nickel is multistage solvent extraction processing. This paper describes a different but simpler treatment technology. The proposed technology has been applied to cobalt/nickel hydroxide intermediate solids produced from the treatment of Electrochemical Machining (ECM) waste sludge, The process consists of dissolving the cobalt/nickel hydroxides in basic cyanide solutions. Cobalt and nickel form aqueous .solution metal cyanide complexes. Nickel can be selectively precipitated from the solution as a nickellic hydroxide solid. Cobalt can be recovered from the leach solution by precipitation of a cobaltous/cobaltic cyanide double salt. The double salt product can then be subsequently treated to produce an appropriate cobalt product. The process chemistry, proposed fiowsheet and preliminary reagent costs are presented and discussed.

Jan 1, 1998

By J. -S. Park, H. -S. Jeon

This study has been carried out to develop a relatively simple hydrometallurgical process for recovering nickel as nickel sulfate from the spent nickel-cadmium battery residue in which cadmium was removed by vacuum distillation. This residue is composed of 36 % nickel, 20 % iron, and other metals such as cobalt. First, crushing and selective classification were performed to separate iron to produce a nickel-rich product (over 40 % nickel). This product was dissolved in sulfuric acid to obtain a nickel sulfate solution. During the dissolution, nitric acid and air were added to the system to enhance the iron oxidation reaction rate. The free acid remaining in the dissolved solution was neutralized by adding nickel carbonate. Iron was precipitated as iron hydroxide and removed from the solution. The nickel sulfate solution was then fed to a vacuum evaporator to concentrate the solution by evaporation of water and crystallized at around 45°C to obtain nickel sulfate hexahydrate. A recrystallization process could remove other impurities such as zinc and manganese.

Jan 1, 2000

By Jenq-Gong Duh, Jyh-Wei Lee

"Hard chromizing process is a method for developing a surface modified coating providing wear, corrosion resistance and high temperature surface protection. Two carbon steels with 0.45 wt% and 0.95 wt% carbon contents, respectively, were chromized with pack cementation process at 950'C for 4 and 9 hours, respectively. The phase transformation and microstructure phenomena of chromized coating layer and matrix of two steels were studied with X-ray diffractometer and electron probe microanalyzer. (Cr,Fe)23C6 and (Cr,Fe)7C3 carbides and (Cr,Fe)2N1-x nitride phases were observed on the chromized surfaces. The thickness of chromized layers obeyed the parabolic rate law. The mechanism and diffusional kinetics of the chromizing process were proposed. The diffusivity of chromium in the (Cr,Fe)7C3 carbide phase was calculated using the moving boundary method.IntroductionChromizing process is one of the surface treatment technologies that can produce a chromium contained surface layer with sufficient corrosion and wear resistance on the steel matrix [1-7]. The relatively low cost and no ""line-of-sight"" restrictions are main advantages of chromizing. Adequate bonding strength of these coatings to the substrate was reported [7]. Chromizing process can be classified into soft chromizing and hard chromizing [2]. Soft chromizing is applied to steels containing less than 0.1wt% carbon through which chromium will be diffused. High temperature oxidation resistance improvement is the main purpose of soft chromizing process. On the contrary, the hard chromizing can be applied to steel containing more than 0.3wt% carbon, and very hard chromium nitride and carbide layers will be formed on the surface, which are very resistant to wear, corrosion and temperature [5-7]. In the previous studies on the Fe-Mn-Al-Cr alloy [5,7] and carbon steels [6], the thickness (X) of chromizing layers was analyzed and found the parabolic rate Jaw prevailed:"

Jan 1, 2004

By G. C. Yao

Iron and silicon impurities can form needle and branch shape intermetallie compounds in molten aluminum when there is no manganese. It is difficult to separate them from molten aluminum by electromagnetic separation. The Fe-Si-AI and Fe-AI intcrmetallic compounds were transformed into Mn-Fe-Si-AI and Mn-Fe-AI compounds by the addition of manganesc into molten aluminum, In molten aluminum the morphology of these intermetallic compound particles is lumpish and spherical. Migration resistance of these impurity particles is small, which is beneficial to separation. FeSiMnAl4 and FeMnAl6 arc paramagnetic. These impurity particles can be moved by magnetic force and can be separated from the molten aluminum.

Jan 1, 2003

By M. D. Stephens

A new, one-step process for extracting titanium from titaniferrous materials has been demonstrated. In the process, depleted uranium tetrafluoride (DUF 4), a solid, is mixed with ilmenite (FeTi03) and heated to 900°C. Titanium is extracted in the vapor phase as titanium tetrafluoride (TiF4) and the DUF4 is converted to uranium-iron oxide. The process has been found to selectively fluorinate the titanium in ilmenite and is capable of producing high purity TiF 4 with very low iron content. TiF 4 can be collected by condensation or through reaction with a fluoride salt such as NH4F, KF, or NaF. The TiF4 produced from the process can be used to make titanium metal, titanium oxide, or fluorotitanate compounds. Since the fluorination process is highly selective for titanium, it avoids many of the separations and waste issues common to other titanium extraction processes.

Jan 1, 2001

By P. Chris Pistorius

"Ilmenite smelting involves partial reduction of iron oxide from a slag consisting mainly of T1O2, T12O3 and FeO, yielding as products iron (with approximately 2% carbon) and titanium slag. Slag purity requirements preclude any fluxing additions, and the aggressive nature of the slag necessitates a furnace freeze lining. Large departures from thermal and chemical equilibrium hold in the smelter, with possible implications for process stability. The slag is approximately 150K. hotter than the metal, which means that the metal temperature is below the slag melting point; this difference in temperature has been shown to lead to formation of a solid TisOs-rich layer between the slag and metal. Recent equilibrium measurements have confirmed that the slag and metal are not in chemical equilibrium either, with significantly more reducing conditions in the metal than in the slag. After solidification, the pseudobrookite slag structure is metastable below approximately 1400K, and may transform upon slight oxidation.IntroductionThe natural mineral ilmenite is the main source of titanium, which is mainly used to produce Ti02-based pigments. Ilmenite has the ideal formula FeTiC>3, but natural minerals can be partially oxidized (to contain some Fe3+), and typically contain MnO and MgO as well, together with associated silicate minerals. Smelting is one of the methods to upgrade ilmenite for subsequent T1O2 pigment production; smelting involves partial reduction of FeO to form metallic iron as a byproduct and titanium slag as the main product. Reduction is typically controlled to yield a slag which contains around 10% FeO, 85% (Ti02+Tij03) and 5% impurity oxides (mainly MnO, AI2O3 and S1O2). An example of a typical average slag composition from reduction of South African ilmenite is shown in Table I. As this indicates, a significant side reaction is reduction of some T1O2 to T12O3. The relative extents of reduction of FeO to Fe and of Ti02 to T12O3 are such that the slag stoichiometry is close to that of the pseudobrookite phase [1]. Pseudobrookite has the structure AB2O5 (where ""A"" and ""B"" are different cation sites); the phase which makes up the bulk of solidified titanium slag has the AB2O5 structure and stoichiometry [2], and can be viewed as a solid solution of FeTi20s, T13O5, ÌçÔÀ2è5, MgTi20s, AI2T1O5 and C^TiOs [1]. This solid-solution phase is referred to as ""pseudobrookite"" or ""M3O5"" in this paper."

Jan 1, 2012

By Mariane Costalonga de Aguiar, Carlos Mauricio Fontes Vieira, Sergio Neves Monteiro

"This work evaluates the effect of incorporation of an ornamental rock waste into an industrial clayey body used for roofing tiles fabrication. Formulations with 0, 10, 20 and 30 wt.% of waste were prepared by replacing the sand in the industrial clayey body. The plasticity of the formulations was determined by the Atterberg limits. Specimens were fabricated by 18 MPa press-molding and then fired from 850, 950 and 1050°C. The specimens were tested to determine the water absorption, linear shrinkage and three points bending flexural strength. The results indicated that the waste improves the extrusion performance of the clayey body by decreasing its plasticity. The use of the waste was beneficial to the water absorption and mechanical strength of the fired clayey ceramic at 1050°C.IntroductionOrnamental rock is a natural resource available in the municipal area of Santo Antonio de Padua and located 150 km from the city of Campos dos Goytacazes, northe of state of Rio de Janeiro, Brazil. Intense industrial activity related to ornamental stones, especially gneisses, is traditionally occurring in the region. After mining, the flagstone is submitted to sawing to obtain blocks and then, after a manual operation, the final products are small flagstones [1,2]. During the sawing operation, a sludge composed of water and fine particles of rock is generated. A monthly production of 1000 tons of ornamental rock waste is estimated to be produced at Santo Antonio de Padua. The final disposal of this waste has brought serious environmental problems. Since most industries do not have an adequate sludge treatment, the waste is contaminating the soil and underground waters as well as obstructing rivers and lakes.Ceramic bodies industrially fabricated in the municipal area of Campos dos Goytacazes, 280 km from the city of Rio de Janeiro, are still empirically elaborated using a mixture of local clays. These clays are predominantly kaolinitic mineral, associated with high plasticity. Due to the excessive plasticity of the ceramic bodies, it is common to have dimensional defects in the final products after the drying and firing processes. Moreover, the kaolinitic structure and the presence of aluminum hydroxide confer a refractory behavior to the local clays. This impairs sintering during the firing operation. In the case of clay ceramics for civil construction, this results in greater porosity associated with elevated values of water absorption [3,4]. To avoid this problem, it is necessary to reformulate the ceramic body composition. The addition of both non-plastic materials to reduce plasticity and fluxes to condition the refractoriness is a possible alternative."

Jan 1, 2011