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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

A novel, low-pressure adaptation of Praxair?s coherent jet technology utilizing CoJet lances was developed for application at Inco&apos;s Copper Cliff Smelter where oxygen is available in large tonnage quantities but only at relatively low supply pressures (< 193 kPa header pressure). The project objectives were to evaluate the effect of coherent jet technology on controlling oxygen lance accretion (?horn?) formation and to increase oxygen efficiency in the Inco Oxygen Top-Blowing Nitrogen Bottom Stirring (TBBS) MK Reactor used for converting nickel- contaminated chalcocite to semi-blister copper. This paper describes the development and subsequent implementation and testing of two CoJet lances in this application.

Jan 1, 2005

By Maurizio Marezio Bertini

Ammonia - ammonium sulfate solutions were sparged in a glass reactor with a SO2/O2 gas mixture (2% SO2 and 98% O2) to leach copper from pure chalcopyrite and chalcopyrite concentrate. The SO2/O2 mixture produces higher and faster extractions than O2 by itself. The effect of temperature, particle size and free ammonia concentration was investigated. The fastest and highest recoveries were obtained at 80 oC from a chalcopyrite concentrate with a d80equal to 13 m, with about 83 gpl free ammonia, an average pH equal to 8.75 and a stirring speed of 500 rpm. The extraction process was controlled by diffusion through a product layer, according to the shrinking core model, with an activation energy of 41 kJ/mole.

Jan 1, 2003

By John P. Hager

One possible approach for the recovery of mercury from acid plant blow-down sludge in smelters is the use of a vacuum retort reactor for the vaporization of the mercury with subsequent collection of metallic mercury in an attached condenser. An experimental study was undertaken to investigate the vaporization of mercury when present as a compound in the Hg-S-O and Hg-Se systems. A transpiration reactor was modified to operate under reduced pressure and with a continuous flow of inert sweep gas. A water-cooled cold finger was inserted into the exit end of the reactor to provide for the rapid quenching of the exit gases and the collection of the mercury. Rates of vaporization were measured at several temperatures for each compound and were generally found to be constant at a given temperature and reactor pressure. The results were used to determine the minimum operating temperature for 100% vaporization of the compound in 60 minutes. For Hg2SO4, HgSO4, and HgSO/2HgO the required temperatures. for a reactor pressure of 50 Torr. were determined to be 634°, 622°. and 603°C. respectively. For HgO, HgSe, and HgS the required temperatures were 557°. 451°. And 382°C. respectively. For HgS the rate of vaporization was also measured at a reactor pressure of 1 00 Torr. The rate of vaporization was found to be slower resulting in an increased vaporization temperature of 423°C. It was also determined that the mercury vapor present in the exit gas stream can back-react with the other gas species to a significant extent and can result in very little condensed metallic mercury. For the vaporization of both HgS and HgSe. the mercury vapor was found to have back-reacted to the extent that virtually none of the vaporized mercury was collected in metallic form. For the vaporization of Hg2S04? HgS04, and HgSO4*2HgO the amount of metallic mercury recovered varied from approximately 50% for HgS04*2HgO to approximately 10% for Hg2S04 and HgS04. Only for HgO was the recovered mercury in primarily elemental form. The application of the results to the operation of a vacuum retort and condenser system is discussed.

Jan 1, 2001

By M Kolbe

Co-Cu exhibits a metastable miscibility gap in the region of the undercooled melt. Specimens have been undercooled and solidified containerlessly into the metastable miscibility gap in an electromagnetic levitation facility (EML) and in drop tube (DT) experiments. Due to the high undercooling the velocity of the solidification front is very high and the microstructure is frozen in instantaneously. The microstructure of samples processed in the EML is influenced by the electromagnetic stirring due to the induction of electrical currents into the melt. A variety of microstructures has been observed. After undercooling below the binodal the liquid melt separates into the Co-rich L1-phase and the Cu-rich L2-phase. Two basic morphologies of the L1-phase can be observed, they can be attributed to the transition in dendrite growth from diffusionally and thermally controlled to only thermally controlled growth. Transient microstructures are observed after solidification in the vicinity of the binodal. Drop tube experiments, which lead to a rapid solidification of a distribution of droplets under reduced gravity conditions, in contrary allow for the observation of the early stages of demixing: the microstructure shows a homogeneous distribution of spherical particles of the minority phase in the droplets. The cooling rate of the droplets and its dependence on the droplet radius has been calculated. The solidification velocity as a function of undercooling has been measured in the EML for the composition Co-lB.Bat%Cu. The data are analysed in the framework of the LKTlBCT model with a velocity-dependent distribution coefficient as well as within a model of Galenko and Danilov using a kinetic growth coefficient of u=0.22 m/Ks.

Jan 1, 2002

By Jiang Diao, Yong Qiao, Xuan Liu, Tao Zhang, Bing Xie

The equilibrium experiments between the FeO-SiO2-MnO-TiO2-V2O3-Cr2O3-MgO slag system and solid pure iron were performed to investigate the vanadium and chromium distribution ratio under Ar atmosphere. The influence of w(FeO), w(V2O3) and w(Cr2O3) in slag on vanadium and chromium distribution ratios were studied at 1653 K. The experimental results were compared with calculated distribution ratios based on molecule and ions coexistence theory. Both of them showed that higher FeO content in slag would improve the distribution ratios of V and Cr between slag and hot metal. The distribution ratio of Cr or V increased with the increase of Cr2O3 or V2O3 content, respectively. To optimize the oxidation of V and Cr from hot metal, a high oxidizing slag and suitable content of Cr2O3 and V2O3 in the slag were recommended. The results provided reference for the further study on the extraction of V and Cr in VTi magnetite.

Jan 1, 2016

By Cao rong-jiang, Tang Xin-he

"In ordinary manufacture process of tungsten powder, a preferable intermediate product used is ammonium paratungstate (APT). The particle size of tungten powder made from it through W2OO58 is larger than 1. 0 um. In order to obtain ultrafine tungsten powder with narrow size distribution, a new type of tungstate, hydraziniull tungstate, was studied. Its formula is 5(N2H5)2O·12 WO.s , with tetragonal crystal structure of a=5.821 , c=18. 468. Three methods for preparing hydrazinium tungstate (ART) were set up and ART can be produced by current industrial APT process with little modification of operation and without any change of equipment.Under certain PH and operation condition of the solution from which ART was produced, an autoreduction of tungsten occured, which produced a lower valency tungstate with blue color when ART was heated at different temperatures, in N atmosphere, tungsten bronze, tetragonal W0290 and W02.7E could be obtained respectively. They all have the superiorities, in the production of tungsten powder, of superfine size and narrow size distribution [average size of 0.5um or even smaller.The rate of autoreduction of ART is very fast at elevated temperature. The reduction reaction, which gaves tetragonal WO290, could be handled smoothly without explosion. To research their behaviors at autoreduction temperatures and the products of autoreduction will be new advances of tungsten chemistry and may also serve tungsten industry with new processes and materials."

Jan 1, 1988

By A. Navarra

Peirce-Smith converting (PSC) is applied for roughly 50% of primary nickel and 70% of primary copper production. PSC cycles produce batches of ironfree sulfide matte (or blister copper, in the case of copper smelters), that are subject to further processing. However, the number of cycles that can be performed simultaneously is limited by the offgas handling system. Moreover, PSC suffers from variation in the yield and duration of the cycles. This variation is managed by conventional smelter designs, in which the upstream smelting capacity exceeds the nominal converting capacity; PSC is thus a major bottleneck in conventional nickel and copper smelters. Stabilization and standardization of PSC operations can therefore increase smelter throughput. The current paper presents a discrete event simulation (DES) framework to assist in smelter debottlenecking. It features random number generation to represent cycle variability, and time-adaptive finite differences to represent thermochemical complexity. Preliminary computations are presented.

By T. Asahina, M. Nakamura, M. Mabuchi, I. Shigematsu, M. Nakanishi, G. Yamauchi

"Commercial stainless steels (SUS304L and SUS430) were subjected to equal channel angular extrusion (ECAE) at room temperature to a total strain of 2.3 to 9.2. For each type of stainless steel, it was shown that the sample processed by ECAE showed higher room temperature strength than the as-quenched sample. This is probably due to the heavily worked structure. On the other hand, both strength and elongation of the ECAE processed SUS430 were increased by annealing at 773K. It is likely that higher strength is attributed to both the heavily worked structure and fine substructures. It is also likely that higher elongation is attributed to the fine substructures. It is concluded that ECAE is available for improving the room temperature strength of commercial stainless steels.INTRODUCTIONEqual channel angular extrusion ( ECAE ) is a technique that provides the repetitive deformation and allows to high intensity of deformation. With this procedure, a sample is pressed through a channel that has an equal cross section but bent at an angle of ?> [1-2]. Shear strain is introduced when a sample passes through the bending point of the channel. Repetitive processing is feasible because the cross-sectional dimension of a sample has no change during processing. To date, many reports have described that ECAE is available for the fabrication of fine-grained materials [3-14]. On the other hand, an ECAE processed sample can achieve high intensity of deformation through repetitive deformation. According to the equation given by Segal [ 2 ], a strain of about 1 is introduced in each pass through die if the angle ? is 90 deg.It is well known that high tensile strength can be achieved in metallic materials through work hardening [15]. It is also known that metallic materials with fine grain size show high strength [16]. Hence, it is expected that ECAE is available for strengthening method in metallic materials. In the present paper, we will report the mechanical properties of stainless steels processed by ECAE. As samples, SUS304L austenite stainless steel and SUS430 ferritic stainless steel were chosen. Each alloy has a single-phase structure (fee or bee) and shows no phase transformation, so that transformation strengthening cannot be applied. Hence, a heavy cold work such as ECAE may be effective for strengthening of this stainless steel. Annealing was conducted for the ECAE processed SUS430 to vary its microstructure. Then, the effect of annealing on the strength of the ECAE processed SUS430 was also investigated."

Jan 1, 2000

By Rikiya Kamezawa, Rudiono, Manabu Takeuchi

"Schottky type solar cells based on phthalocyanine (Pc) thin films were fabricated, and their photovoltaic performance was investigated in various ambient atmospheres. Most of cells prepared in this study showed a good rectification and photovoltaic effects in the visible wavelength region. The introduction ofN02 gas into the measuring chamber was confirmed to increase the current both in dark and under light illumination. However, chemical reaction between the Al electrode and N02 formed some oxide and deteriorated the Schottky barrier, resulting in an increase in cell resistivity. SF 6 gas also showed similar effects on the cell performance.IntroductionPhthalocyanine is one of the typical organic semiconductors, which shows high photoconductive sensitivity in the visible to infrared region. Today, several kinds of metal phthalocyanines are used in electrophotographic photoreceptors. In addition, application of phthalocyanines to solar cells have also been trying by many workers [1, 2]. Many efforts have been made for improving performance of phthalocyanine solar cells by modification of device structure [3, 4], doping by dye or pigment [5, 6] and incorporation of metal clusters [7]. It is known that electrical conductivity in phthalocyanine is increased by adsorption ofNO2 [8, 9]. We tried to improve photovoltaic performance ofphthalocyanine solar cell by adsorption ofNO2. This paper describes the influence of N02 adsorption on the photovoltaic behavior of phthalocyanine solar cells."

Jan 1, 2000

By Rzyman Michal, Nakamura Takashi, Shibata Etsuro, Grabda Mariusz, Oleszek-Kudlak Sylwia

"Tetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in many materials such as plastics and textiles. Thermal degradation of BFR containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3. Our thermodynamic considerations indicate that these gases can act as bromination agents for metallic oxides such as ZnO, Cu2O, CuO, PbO and FeO. Moreover, these metallic oxides have the thermodynamic tendency to brominate easier than does Sb2O3. The aim of this study was to investigate experimentally the reactivity of ZnO with 1) HBr originating from the thermal decomposition of TBBPA and 2) SbBr3, which is formed during thermal degradation of brominated flame retardant plastics. The thermal treatments of the mixture of compounds of interest were investigated by thermogravimetry coupled with mass spectrometry.IntroductionTetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in materials such as plastics and textiles. For instance, 4.5 million tons of flame retardant plastics containing BFRs are produced in Japan each year. Thus, in thermal treatments such as the incineration and melting of solid wastes, BFR containing plastics are intentionally or unintentionally included in the wastes. Thermal degradation of BFR-containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3 [1-5]. Our thermodynamic considerations [6] indicate that heavy metal oxides such as ZnO, Cu2O, CuO, PbO and FeO should easily react with HBr prior to Sb2O3 and also with SbBr3, the main gaseous product in the thermal decomposition of TBBPA, forming low boiling point metallic bromides suitable for the volatile separation of heavy metals. The metal oxides are also expected to qualitatively and quantitatively affect debromination and decomposition of the flame retardant."

Jan 1, 2008

By P. H. Chang, J. E. Gould

"Solidification structures and austenite decomposition in some spot welded O.05%C - O.3%Mn steels have been studied with the aid of a numerical thermal model. The model is a one dimensional finite difference formulation, and accounts for melting, temperature dependent thermal properties, effective heat transfer in the liquid, and contact resistances. The model was used to predict solidification conditions during resolidification of the nugget. These solidification conditions were correlated with the primary dendrite spacing using available primary dendrite spacings modelling. The model was also used to predict cooling rates in the temperature regime for austenite decomposition. These cooling rates were used to interpret the underlying microstructure.INTRODUCTIONThe metallurgical transformations which occur during the spot welding of low carbon steels have traditionally been characterized only in the most general of fashions. This is most probably due to the similarity of spot welded microstructures to other welded microstructures, and that the mechanical integrity of spot welds has not been a concern. In addition, little information about the particular thermal cycles experienced during spot welding has been available. The introduction of HSLA (microalloyed) sheet steels has, however, raised new concerns about the integrity of spot welds. These steels have on occasion shown irregular weldability, as well as brittleness in the weld nugget on destructive testing l - 4 .In response to these concerns, considerable work has been done attempting to characterize thermal cycles in spot welds 5-12. This has largely taken the form of thermal modelling, with the end purpose generally to estimate the size of the nugget formed. This work uses the thermal model developed at Inland Steel 13 ,14 to try and understand, in a more fundamental way, microstructural evolution in spot welds. Two facets of this microstructural evolution are examined in detail:"

Jan 1, 1986

By Nickolas J. Themelis

Nearly thirty two million tons of municipal solid wastes (MSW) are combusted annually in over one hundred U.S. Waste-to-Energy (WTE) power plants, thus reducing the use of fuel oil by about 1.6 billion gallons of fuel oil One of the advanced WTE processes is the 0.9-million ton/y SEMASS facility at Rochester, Mass. Most of the combustion in the three giant combustion chambers occurs while the injected shredded wastes are in suspension, i.e., in flash combustion mode. The velocity, temperature, and concentration profiles in the SEMASS combustion chamber were simulated by representing the combustible fraction of MSW by the simplified formula C6HIO04 and using the CFD program Fluent to solve the turbulent energy and mass transport equations. After validation against plant data, this model will be used to examine options for increasing the productivity of WTE combustion chambers, such as optimum distribution of primary and secondary air and oxygen enrichment.

Jan 1, 2003

By Jianxun Song, Hongmin Zhu, Qiuyu Wang, Jungang Hou, Shuqiang Jiao, Xiaobo Zhu

This work presents the results of a study on the Ti3+/Ti2+ couple redox potentials vs. Cl–/Cl2 at the temperature range (673 to 1073 K) in fused LiCl-KCl eutectic by direct potentiometric method. Initial concentrations of TiClx in solvents did not exceed 5.0 mol%. Basic thermodynamic properties of the reactions TiCl2+1/2Cl2(g)=TiCl3 were calculated using the temperature dependencies of apparent standard potentials of the couples E* Ti3+ /Ti2+.

Jan 1, 2014

By Xin Wang, Hongmin Zhu, Shuqiang Jiao

"The behavior of electrochemically depositing silicon in a molten high-melting-point fluoride electrolyte was studied at 1300 °C. The cathodic product was characterized by XRD, SEM and EDS. Though the analysis of structure and composition of deposition, it could certify that silicon deposited on the Mo rod and alloyed with molybdenum. A series of tests had been performed on the cathodic behavior of Si4+ ions in BaF 2-CaF 2-Na2S iF 6 molten salt. The influence of electrochemical parameters on the cathodic deposition of silicon was also investigated. The electrochemical behavior of Si4+ ions in applied fluoride melts was observed to proceed according to one-step reaction.IntroductionGreenhouse warming has been a serious global issue. lt is increasingly urgent for clean and renewable energy. Effective utilization of clean and inexhaustible solar energy has become very important. Solar cell (especially poly-Si solar cell) production has significantly increased this decade, as there is a growing demand for clean energy. Since the early 1980s, the annual growth of the photovoltaic (PY) solar cell industry is more than 30%. More than 90% of the annual solar cell production is based on crystalline silicon wafers. This rapid growth leads to a shortage of silicon of the adequate quality and price for the continued growth of this industry [I , 2J. The most conunonly used technology to produce silicon is the so-called Siemens process. This technology, involves the forming of gaseous Si compounds such as trichlorosilane (SiHCli) or silane (SiH4) with subsequent thermal decomposition of these back to Si. This technology is associated with transformations from solid to gas, and then back to solid phase, which lead to high irreversible thermodynamic losses and subsequent high energy consumption, the energy cost being around 200kWh/kg Si [3l_ The purity of the material from this process is very high (9 to 11 N). In general, what is needed for solar cell purposes are reported to require 4 to 6 N quality. To promote continued growth of the silicon-based PY industry, there is need for a low-energy silicon production process which can produce large amounts of silicon with an acceptable quality and a lower price particularly."

Jan 1, 2012

By Florian Kongoli

Slags and fluxes are important interchangeable dimensions of pyrometallurgical processes. They can increase the efficiency of the smelting, converting and refining processes and improve the quality of the final products. A good slag should have appropriate physicochemical properties such as low liquidus temperature, optimal viscosity, maximum ability to attract undesirable elements, minimum potential of attracting valuable elements, etc .. A good flux, on the other hand, when properly used, can considerably improve the physicochemical properties of the slag since by modifYing its chemical composition it could decrease the liquidus temperature, improve viscosity etc.. Consequently, the choice of a good slag and the corresponding fluxing strategies has become indispensable in most of industrial processes. However, the properties of multi component slags as well as the effect of several fluxes are known only empirically and confusion exists in the literature and in the industrial practice. In today&apos;s reality of frequent changes in the composition of raw materials and that of the fluxes themselves, in the existing or new developing technologies, the quantification of the thermophysicochemical properties of multicomponent slags and the effect of fluxes becomes indispensable. This paper reviews some of the work carried out by the author&apos;s group during the last ten years on the quantification of the thermophysicochemical properties of multicomponent slags and on the effect of fluxes in several smelting and converting processes in close relation to their individual characteristics. Several examples have been given in order to demonstrate the fact that when taken outside the context some fluxes can become in fact anti-fluxes.

Jan 1, 2003

By M. Ramprecht, M. Wu, A. Kharicha, A. Ludwig, H. Holzgruber

"The influence of the frequency of AC power supply on the magneto-hydrodynamic during the electroslag remelting process is studied. The focus is on the electrodynamic field and its resulting mechanical effects on the flow and liquid interfaces. The possible influence of the electrochemistry on the droplet formation is qualitatively discussed.IntroductionThe electroslag remelting (ESR) process is a secondary melting technique which can be used for a variety of metals and alloys, provided appropriate fluxes (slags) and melting parameters are employed. The ESR process is presently operating mostly with AC current of about 50 Hz. However for reasons primarily of inductive losses in the electric circuit, furnaces for ingots larger than 1 m, use or are projected to use current of very low frequency (< 5 Hz). Effects of lower frequencies (2.5-5Hz) on macrostructure and non-metallic inclusions were recently studied by Chang [1]. Most of investigations were performed either with DC power or with AC of 50-60 Hz [2-4]."

Jan 1, 2012

By Elli Nurminen

Sulphate decomposition was studied in the conditions of a typical copper flash smelting heat recovery boiler. The aim was to determine the kinetics of the copper sulphate decomposition reactions and to find out if they are likely to take place in the process conditions prevailing in an industrial HRB. The information is essential in CFD-modelling of the reactions taking place in the boiler and for optimising the process. Thermal decomposition of sulphates was studied by thermogravimetry. The experiments were conducted with a commercial copper sulphate, a partially sulphated copper oxide and an actual process flue dust. The main variables studied were temperature and gas composition of a N2-O2-SO2-mixture. The samples were characterized with SEM, optical microscope and XRD. Temperature affected the decomposition rate strongly but the gas composition had a minor effect on the kinetics. The decomposition was fastest in the partly sulphated oxide and slowest in commercial copper sulphate. Keywords: Sulphate decomposition, flash smelting, heat recovery boiler, flue dust

Jan 1, 2004

By M. Z. Mubarok

Effect of single addition of a lignin-based biopolymer additive, DP 2782, at various dosages as well as in combination with thiourea on cathode polarization during copper deposition was investigated by performing potentiodynamic and galvanostatic measurements using a potentiostat. The result of electrochemical measurements was compared with the behaviour of cathode deposition with glue and thiourea additives. Surface micro-appearance of the copper deposit after 1 h galvanostatic scan under current density of 330 A/m2 and various additive type and dosage was evaluated by scanning electron microscopy (SEM) examination. It was found that the addition of 2.5 mg/l biopolymer gave sufficiently polarizing effect of copper deposition. SEM examination of the cathode surface after galvanostatic scan revealed that the combination of the biopolymer with thiourea (2.5 and 3.5 mg/l) resulted in a compact deposit which is comparable with that resulted from the test with glue and thiourea.

By W. G. Davenport

Chapter 6 examined autotherrnal smelting of pure chalcopyrite concentrate with 50 mass% O2-50 mass% N2 blast. It showed that production of 1500 K products with this blast requires: 181 kg of pure oxygen 337 kg of air per tonne, of concentrate. It also showed that the grade of matte produced with this blast is 58% Cu. This chapter re-examines autotherrnal smelting by asking: (A) WHAT COMPOSITION BLAST (MASS% 02 -MASS% N2), 298 K, WILL AUTOTHERMALL Y PRODUCE 65% Cu MATTE 1500 K FROM PURE CHALCOPYRITE CONCENTRATE? (B) HOW MUCH PURE OXYGEN AND AIR WILL BE NEEDED? These are important questions for flash? smelting because furnace operators usually want to send specific composition matte to converting. This chapter shows how a specified matte can be produced autotherrnally with 298 K oxygen-air blast. Later chapters show how it can be done with hot blast, hydrocarbon combustion, different concentrates etc.

Jan 1, 2001