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By Alejandro R. Alonso, Lizet Alvarado, Gretchen T. Lapidus

"Cobalt and lithium recovery from spent Li-ion secondary batteries has been increasingly studied in recent years due to the high value of both metals and the low proven reserves for lithium. The standard method employed until now has been the deactivation and crushing of the batteries, followed by leaching of the L1C0O2 spinel from the battery cathode using acid solutions, such as 1.5 to 2.0 M HC1 or H2SO4, in a temperature range from 120°C to 250°C. Once leached, the cobalt is separated by electrodeposition and the lithium by precipitation, using large amounts of carbonate to bring the solution to alkaline pH values. In the present work, citric-thiosulfate solutions are used for the spinel leach at room temperature, favoring a reductive environment at room temperature, which stabilizes the cobalt(II) as cobalt citrate and lithium(I) at pH 5, and recovers approximately 99% of both metals.IntroductionThe Li-ion batteries industry has become an important economic sector in recent years. This type of battery is the most promising system for energy storage, because of its high efficiency in charge-discharge cycles, and its adaptability to many configurations. The demand will probably increase because of the need for mobile energy sources in many types of devices ranging from cell phones, tablets, and laptops to medical, navigation and sophisticated communication equipment and even in automobiles.One major problem related to the use of these batteries is the method employed for recycling the components, mostly cobalt and lithium. Currently, there are two processes employed on an industrial scale: the Sony/Sumimoto process, used since 1990 [1] and the Toxco Process [2]. In the first case, incineration is used to open the batteries and at same time volatilize the organic solvents. After that, the metals (copper, iron and aluminum) are physically separated. The cobalt and lithium are recovered as oxides and then thermally treated in order to recycle them for new batteries manufacture."

Jan 1, 2012

By Geysen. Daneel

Better slag valorization is part of improving the sustainability of steel, stainless steel and non- ferrous metal production processes. Besides, it can improve the sustainability of other products and production processes as well. A sound and well established slag valorization is beneficial for the overall economics, marketing and appreciation of the metallurgical process and its products. On 6-7 April 2009, the First International Slag Valorisation Symposium was held in Leuven, Belgium. This paper gives a brief summary of the symposium, providing an overview of slag valorization opportunities. The authors believe that high temperature process slags can have interesting applications and that within the next 10 to 20 years slags will need such valorization options in order to compete with other materials and get general support for further production. On the other hand, the authors also expect a higher demand for slags for the production of various materials. High temperature processes should anticipate on the growing opportunities for valorization of slags and increase the resilience of their process by better understanding slag processing, slag quality and material requirements. More interdisciplinary research efforts are required to reach this level of knowledge for the different high temperature processes. Such an interdisciplinary research platform was recently established at KULeuven, Belgium, named SMART-PRO2 (Sustainable Materialization of Residues from Thermal Processes into Products).

Jan 1, 2010

By R. P. Tavares, M. Isac, R. I. L. Guthrie

"The configuration of the metal delivery system used in twin-roll casting can play a significant role in determining both internal and surface quality of the strips produced by this process.In the present work, a mathematical model for coupled turbulent fluid flow, heat transfer and solidification was developed and used in the study of metal delivery systems for twin-roll casting of low-carbon steels. This study was applied to a pilot twin-roll caster being investigated in Canada, with a roll radius of 0.3 m, producing strips of thicknesses from 4 to 7 mm, at roll speeds ranging between 4 and 12 m/min. Various configurations of metal delivery systems were simulated and their effects on the advance of the interdendritic solidification front and levels of turbulence and temperature within the caster investigated. According to the predictions of the model, an extended nozzle with inlet flow towards the surface of the rolls seems to be the best alternative for feeding liquid steel into twin-roll casters.A full scale water model of a pilot twin-roll caster was also built and used to qualitatively validate the predictions of the mathematical model.Various techniques for fluid flowvisualization were applied. In general, the predictions of the mathematical model were in reasonable agreement with the experiments with the water model."

Jan 1, 1999

By Yoshinao Kobayashi

he removal of oxygen from titanium and zirconium is important for use in application because it significantly affects the mechanical and physical properties such as ductility and toughness. However, thermodynamic properties of oxygen in molten titanium and zirconium have not been clarified and the effective deoxidation process of molten titanium and zirconium has not been established. In this study, the standard Gibbs energy of reaction of oxygen and yttrium in molten titanium and zirconium have been measured by a chemical equilibrium technique. Molten titanium, zirconium, and their alloys with aluminum were equilibrated with a Y2O3, A12O3, or Zr02 pellet in a cold crucible. The results are summarized as follows:

Jan 1, 2000

By N. Kanari

Reactivity of MgO towards C12+air, C12+N2 and C12+CO gas mixtures was studied up to 1000 °C. Carbochlorination of MgO occurs at temperatures lower than that of its oxychlorination. Effects of gas flow rate, temperature and partial pressure of the carbochlorinating gas mixture on the reaction rate were investigated. The apparent activation energy of MgO carbochlorination is 49 kJ1 mol between 425°C and 600°C. At 550 °C, the apparent reaction orders with respect to C12+CO, C12 and CO, are 2.37, 1.47 and 0.89, respectively. At this temperature, the maximum reaction rate was obtained using a C12+CO gas mixture having a Cl2lCO molar ratio equal to about 0.6.

Jan 1, 1998

By Theo Lehner

Turning matte into anodes continues to be an area to watch: for visitors to see pyrometallurgy in action; for metallurgists to keep up with modern smelting furnaces and ever increasing production rates; for management to remain profitable using more tools than taught in school; and for environmentalists to detect the last small clouds from the ever cleaner smelter. Current converting practices have been screened and analyzed, and today, converting and casting is a modern industry. An impressive, though typical learning curve of converter productivity may be detected. Local conditions such as availability and type of raw materials, products extracted, cost factors, etc., have stimulated the development of add-ons or even alternatives to the still dominant method of converting by Peirce-Smith technology. Turning blister copper into anodes follows a similar path, namely increased productivity and improved quality. We dare to predict that development will continue.

Jan 1, 2005

By Frank R. Field, Randolph E. Kirchain, Elisa Alonso

"There are a number of environmental incentives for increasing recycling, including the reduction of waste, energy and resource use. Recycling can also be advantageous for manufacturing firms in both the short and long term. Secondary material can substitute for primary material, potentially dampening primary material price increases and reducing the pressure for greater primary extraction. This paper examines the potential for and dynamics of recycling for the case of platinum using a dynamic, behavioral simulation model of the primary and secondary markets. Since the secondary supply of platinum depends on a supply chain separate from primary extraction, recycling can diversify the risks of primary supply instabilities. Over time, recycling can cut primary consumption, reduce overall costs to firms, and possibly reduce the impact of price fluctuations upon firms.IntroductionThe benefits of recycling, from the perspective of the environment, are many, and the environmental benefits of increased recycling are considered a step towards increased sustainability [1, 2]. Life cycle assessments indicate that obtaining materials from secondary sources generally requires less energy and has fewer environmental impacts than extraction and refining of primary materials [3]. Analyses of materials flows show that, in addition to landfill volume reduction, recycling reduces primary material consumption, affecting long term materials scarcity [4, 5].The benefits of recycling are not limited to the environmental. Firms can benefit from the lower energy costs of recycling, especially that of metals whose primary extraction and refining are particularly energy-intensive (e.g., aluminum). The routine participation by firms in secondary materials markets (e.g., www.recycle.net) shows that this advantage has not gone unnoticed.Recycling can also benefit firms whose costs can be significantly affected by changes in material prices resulting from material shortages and material scarcity, with potentially permanent effects upon firms [6-8]. This paper focuses on the impact of recycling in the face of platinum scarcity for supply chain downstream firms."

Jan 1, 2008

By Wen Liangying, Zou Chong, Tan Xiuqin, Bai Chenguang, Zhang Shengfu

"Eight typical metallurgical byproducts containing iron were selected based on the effect of the chemical composition, particle size, additives on the burnout degree of pulverized coal. Effect of three typical byproducts including fine iron ore, BOF dust and BOF sludge on combustion reactivity and combustion efficiency were investigated using TG-DSC method. The results indicated that the three additives have obvious catalytic effects on pulverized coal. By comparison, the relative active sequence of byproducts to the catalytic combustion can be described as follows: BOF dust>BOF sludge>fine iron ore. Moreover, adding BOF dust as component of additives also shows significant catalytic effects on combustion efficiency during rapid heating process.IntroductionChina is the largest producer in the world with an annual output reaching over 6 billion tons. Solid wastes arising from iron and steel making increases the environment pressure in recently years. For instance, annual output of dust during the production of iron and steel making in China reach up to 5 million tons, which is close to 8%~15% of the amount of steel [1]. Another characteristic of these byproducts is they are finer particle which are just harder to deal with. Since some of solid wastes, including dusts, scales, and sludge, usually contain high iron content, sintering plants have traditionally been used to recycle byproducts in integrated steel plants in China. However these byproducts also have noticeable effects on sinter quality, sinter strength and productivity and, therefore, waste recycling is limited depending on the analysis of the waste materials [2]. Another method which is pre-treatment of byproducts in pelletizing process, increases of energy consumption and production cost. In addition, metallurgical byproducts often contain heavy metals and alkalis. For these reasons, recycling rate of the byproducts in China is very low. Therefore, how to recycle the byproducts in iron and steel making process is an important subject."

Jan 1, 2012

By J. L. Liow

Studies have been carried out on the causes and effects of slopping in an annular cylindrical geometry such as the top submerged combustion reactor. Properties of standing waves formed such as the wave profile, period, pressure distribution and velocity have been derived analytically. The wear profile due to wave erosion was calculated based on the assumption of linear motion and that the wear is a dissolution process. The use of the j, factor showed that the wear was proportional to the square root of the wave velocity at any point. Using the dimensions of the lsasmelt reactor given by Errington et al. (1987)[11, the wear profile due to wave erosion was calculated using the analytical solution. The wear profile calculated was shown to have a maximum just below the initial bath surface. The wear was found to be concentrated in the region where the first asymmetric standing wave was most active. The results showed that the refractory near the bath surface will be affected by wave erosion, more so than any other parts of the reactor. The contribution of wave erosion on wear must be accounted for in assessing the total refractory wear of a vessel in which slopping exists.

Jan 1, 1991

By Xuling Chen, Zhiyun Ji, Min Gan, Tao Jiang, Liang Yin, Xiaohui Fan

Straw char exhibited considerably faster burning speed than coke breeze for its porosity, which significantly degraded sinter quality when it replacing coke breeze as sintering fuel. In this investigation, preforming technology has been employed to densify raw straw. The properties of straw char preformed show that its density was increased, and the structure was also densified, which made the difference of combustibility between the straw char and coke breeze smaller. The proper preforming temperature, residence time and pressure were 200℃, 1min and 120MPa respectively. Sinter pot trials show that the product carbonized from preformed straw made the proper replacement ratio to coke breeze increase from 20% to 40%, and the emission reduction of SOx, NOx in flue gas increase from 11.50%, 14.15% to 37.85%, 23.60% respectively, compared with non-preformed straw char.

Jan 1, 2015

By Nathan A. Tiner

Sulfuric acid anodizing process is extensively used in many industrial and consumer products to provide corrosion resistance to aluminum alloys. The anodic coatings produced consist of amorphous alhnum oxide with a pornus structure which is easily sealed and colored with dyes. The coatings may contain defects due to surface flaws, canposition and microstructure of the aluminum alloy, and/or due to the anodizing process conditions. This paper will describe the techniques used in anodizing process, various defects which may be produced in anodic coatings and the methods to control them.

Jan 1, 1992

By M. Bilal Khan

Thermal stress relief by means of a typical heat treatment cycle (660oC for one hr) is compared with the one achieved through vibratory stress relief at resonant and multiple resonant frequencies for the D-406 HSLA material. Our analysis of the data is based on the microhardness profiles measured for the entire length of scales, namely, base metal, heat affected zone (HAZ) and the weld bead itself. The profiles obtained using the two techniques mimic each other, for an equivalent 70% stress relief level. The data are further qualified by impact testing wherein the zone of interest is projected in the retention groove to provide impact by the pendulum striker in the Charpy mode. Higher equivalent energy absorption in the treated specimens confirms the efficacy of the vibratory method. The present work rectifies earlier anomaly where heat treatment has been reported at 310oC for the same material.

Jan 1, 2009

By Christophe Thiébaut

Keywords: Pyrochemistry, Salts Treatment, Distillation The pyrochemical purification of metal generates spent salts. When this metal is an actinide such as plutonium, the slags cannot be discarded and are thus disposed in nuclear facility. In order to handle with these slags, the decision has been taken to reduce stored quantities. The development of a pyrochemical treatment is in progress in the CEA Valduc centre. The feed salt, typically composed of various Pu and Am species contained into monovalent or divalent chloride matrix, is first oxidized to convert the actinides into oxides. Then the chlorides are separated from the actinide oxides by vacuum distillation. Temperatures higher than 750°C for monochloride salts mixture NaCl/KCl and higher than 1100°C for divalent CaCl2 base salts, are required to produce an industrial flow of vaporization. Inactive qualification of the process for NaCl/KCl base salt has been carried out with lanthanide surrogates. Then, a pilot equipment, called distillator has been designed and built for production-scale distillation of NaCl/KCl and CaCl2 oxidized plutonium salts. Industrial flows of vaporization have been obtained with this pilot equipment : about 4 g/cm²/h for NaCl/KCl at 800?900°C and 1 Pa, and more than 1,5 g/cm²/h for CaCl2 base salts between 1000?1200°C at 0.1 Pa. The last step, now in progress, is the integration of the distillator into a glove box.

Jan 1, 2005

By K. Verbeken, E. Wettinck, M. Verhaege

Iron (III) can easily and selectively be removed from acidic sulphate solutions with organo-phosphoric acids like Di-2-Ethyl-Hexyl-Phosphoric Acid [D2EHPA]. Stripping of the iron (III) loaded organic, however, is difficult unless highly concentrated inorganic acid solutions are used. In this paper results are shown for the enhanced stripping of iron from loaded D2EHPA by electro-reduction. The loaded solvent is contacted with a 2 M H2SO4 solution, which is continuously recycled in an electrochemical reactor where iron (III) is reduced to iron(II). As iron (II) is not extracted by D2EHPA, the equilibrium for iron (III)- D2EHPA is shifted towards the aqueous iron (Il)-sulphuric acid solution. The electro-reduction unit is a vessel with separated catholyte and anolyte chambers. The catholyte is the actual stripping solution where iron (III) is reduced to iron (II) on a stainless steel electrode. The anolyte is a 2 M H2SO4 solution where oxygen is evolved on a lead alloy electrode. A sintered glass plug separates the compartments. With this unit, enhanced stripping of iron from the solvent is possible under mild acid conditions [2 M H2SO4], and a concentrated ferrous sulphate solution can be obtained. The results shown have mainly been obtained by studying the parameters affecting the electro-reductive stripping of a D2EHPA loaded organic phase in a batch reactor. From an iron (IH)-saturated 20 vol. % D2EHPA solvent containing ~ 12.5 g/1 Fe (III) over 90% of the iron can be stripped in one stage with a 2 M H2SO4 solution at 50°C. It is shown that in this way it should be possible to obtain a concentrated ferrous sulphate solution which can be processed downstream to recover a pure iron product.

Jan 1, 2000

By Han Yi

The coarse indium ingots produced by Shaoguan smelter contained a lot of impurities. In order to produce the high pure indium with the purity more than 99.99%, the appropriate refining processes were designed and the practice of combined application of Glycerin-KI process and electrolysis in Shaoguan smelter was introduced.

Jan 1, 2005

By Charles A. Sorrell

Two red muds, two fly ashes, and several aluminosilicate minerals were subjected to direct treatment with concentrated H2SO4 at temperatures of 175°C and below. X-ray analysis showed that virtually all the sulfate reaction products remained in the solid residue because of their low solubilities in x SO Substantial portions of the Al2O3 Fe2O3TiO2, Na2O, and K2O components of the materials reacted to form water soluble sulfates, which were then removed by H2O leaching at 55°C. The solid residue after water leaching consisted largely of amorphous silica and, in lime bearing compounds, CaSO4, The reaction and leaching processes were effective in removing all or nearly all the Al2O3. Fe2O3, TiO2, Na2O, and in lime components in the fly ashes, red muds, china clay, bentonites, the nephelioe fraction of nepheline syenite, and a plaster insulating brick composed of anorthite and mullite. Reaction with potassium feldspar and petalite took place, with formation of alkali aluminum sulfates, but the reaction rates and yields were extremely low. Potassium feldspar can be heated with Na2O and x O in air at 700°C for 24 hours, or with CaO at 1000°C for 24 hours, after which the reaction product kaliophilite, nepheline, and leucite-like phases, prove to be very susceptible to H2SO4, reaction and H2O leaching, providing yields near 100% of the Al2O2 content. An alternative method of H SO treatment consists of heating the sample in a silica tube and passing H2SO4 vapor over it. Preliminary results indicate that this method can be effective in enhancing the kinetics of reaction with the Al O component of potassium feldspar and offer the possibility that formation of Al2 (SO ) Fe2(SO4)3 and TiOSO4 can be accomplished selectively by taking advantage of the fact that the upper stability limits of the respective sulfates in the presence of H2SO4 vapor will be different.

Jan 1, 1982

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 William Petruk

A mineralogical and image analysis study was conducted on samples of U tailings from pilot-plant runs on Midwest ore in Northern Saskatchewan. The tailings had been subjected to simulated weathering for the equivalent of 10 years in a tailings facility (lysimeter). The pH varied from 7.0 at the beginning of the test to 5.9 at the end. The results show that during the simulated weathering sane of the gersdorffite, uraninite, galena and pyrite had oxidized, with gersdorffite being the most reactive and pyrite the least. Reaction was evident at the top of the lysilleter , but was most intense at the seepage discharge. sane of the released ions precipitated as Ni, Pb, and U arsenates, sulfarsenates, sulfates and oxides on particles of all minerals. Green crystals of Ni sulfate and white crystals of ca sulfate had precipitated at the surface of the lysilleter. Clay minerals and chlorite had washed from the top of the lysirneter towards the seepage discharge.

Jan 1, 1989

By Milton Manrique, Edgar E. Vidal, Patrick R. Taylor

"Ultrafine zirconium carbide powder has been synthesized using zircon concentrate and methane in a thermal plasma reactor. The effect of several experimental variables, such as power used and zircon particle size, on the conversion has been studied. A thermodynamic analysis of the possible reactions and stable compounds was performed. A mathematical model that describes the in-flight decomposition of zircon particles was developed based on a description of the temperature and velocity profiles calculated in the reactor. It was shown that the formation of zirconium carbide from zircon and methane is thermodynamically possible. Complete 'vaporization of zircon in the reactor is predicted when the particle size is below 45flm and the effective power entering the reactor is 15 kW. The powders were collected and characterized by XRD, SEM, TEM and chemical analysis using ICP. Results of the product analysis indicated the presence of zirconium carbide, zirconium oxide, silicon carbide and silicon oxide.IntroductionIn recent years there has been an increased interest in the production of nanometric sized powders of ceramic materials for use in advanced materials applications. One possible method to produce these powders is with a thermal plasma reactor, which offers high temperatures and fast quenching rates. This technology has been called - Thermal Plasma Synthesis - [1].Zirconium Carbide (ZrCx) has typical properties of transition metal carbides: elevated hardness - between alumina and diamond - a high melting temperature of 3420°C and high chemical stability at room temperature [2]. ZrCx has a Bl crystal structure with deficiencies in the number of carbon atoms in the cell with x between 0.6 and 1 [3]. Different methods have been used to produce ZrC, one method is by direct reaction of zirconium hydride or halide with carbon. Other methods used are direct reduction and carburization of zirconium oxide (Zr02) and reaction of metallic zirconium with a caburizing gas such as acetylene [3]. Recently small films of ZrC have been obtained using a sputtering device [4,5]. ZrC has been used in nuclear plants as a low neutron absorbing and high mechanical resistant refractory material and also as a constituent in cathodes made of UC-ZrC [6]. It is also used in the form of tubes, boats and crucibles to handle molten metals and as part of electronic devices used for thermoionic transducers. Recently ZrC has been used along with zirconium diboride (ZrB2) to produce composite materials [7,8]."

Jan 1, 1996

By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011