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By M. Cavallini, G. Cannavale, P. P. Milella, A. Pescetelli, C. Lupi

Ni-Cd sealed and vented cells have been widely used in the last few years. The environmental hazard related to the heavy metals contained in Ni-Cd batteries is well known. Therefore, a number of scientific studies and commercial processes have been implemented in order to recycle them. Since spent batteries are a heterogeneous and complex material, any kind of recovery process needs some preliminary treatments. The proposed process described in this paper has been tested in laboratory and further developed in a pilot plant. It consists of a combination of mechanical and hydrometallurgical treatment steps, and is able to treat all type of Ni-Cd batteries. In particular, the mechanical treatments have to be done separately on vented and sealed cells, while the hydrometallurgical step is performed on a mixture of the two products obtained from mechanical steps. A fully automated dismantling line would allow the separate recovery of the plastic or metallic casing, terminals, KOH electrolyte, and electrodes to be further processed· for Ni and Cd recovery. The electrodes coming from dismantling line and sealed batteries are submitted separately to an original crushing and elutriation treatment to separate metallic and active paste in the first case and metallic, plastic and active paste in the second case. The hydrometallurgical treatment is carried out on active paste bearing product to produce Ni, Cd, and Fe comn1ercial salts through acidic leaching followed by a multi-step solvent extraction operation to obtain pure solutions.

Jan 1, 2000

By Honggang Zhong, Xin Cao, Qijie Zhai, Hongmei Song, Congsen Wu, Cheng Zhang, Jingzheng Ye

"The influence of superheat on the solidification structure and ferrite/austenite phase transformation of a novel lean duplex stainless steel (DSS) was investigated on a setup, which designed to thermally simulate the continuous casting process. The results showed that the macrostructure of the samples all exhibited chill zone, columnar zone and equiaxed zone. The distance from chill zone to position of columnar to equiaxed transition (CET) moved from 51.0 mm to 39.8 mm with an decrease of superheat from 70 °C to 10 °C, and that the grains in the chill zone tended to be finer. In equiaxed zone, the fme and uniform grains were observed when superheat higher than 40 °C; while, coarse grains were found in samples poured at low superheat. Generally, the volume fraction of ferrite increased along the dendritic growth direction, and stabilized in equiaxed zone. The high superheat decreased the volume fraction of ferrite in equiaxed zone, while it had indistinctive influence on chill zone and columnar zone.IntroductionDuplex stainless steel with approximately equal volume of ferrite and austenite, offering an attractive combination of corrosion resistance and mechanical properties. [ l]. The production of DSS, worldwide application in structural engineering[2] and petrochemical industry[3], have increase by more than 100% in the latest decade[4]. But due to the sharp prices increase of nickel and chromium, lean duplex stainless steels which have lower contents of alloy elements were developed. They perform well in both mechanical and corrosion resistance[S, 6] and even have TRlP(Transformation Induced Plasticity) effect[?]. Nonetheless , the mechanical properties of DSS was affected greatly by the solidification structure, such as columnar to equiaxed transition (CET), grain size and phase content[8]. So, the solidification behavior of stainless steel was investigated widely"

Jan 1, 2014

By K. Iwami, K. Abe

"Onahama Smelter and Refinery has been operated-since 1965 arid currently produces 243,000 metric tons per year of cathode copper. The Onahama tankhouse consists of conventional-type No.1 and 2 tankhouses with the capacity of 123,000 metric tons per year and No.3 tankhouse with 120,000 metric tons per year, adopting jumbo tank system, using hazelett anode respectively.In October, 1996, for the purpose of improving the - anode verticality, new anode copper body press machine has been installed in No.1, 2 tankhouses; by increasing Walker type anode copper weight by 35kg to 365kg. Consequently, it is possible to raise current density from 191 to 222 A/m2 and the No.1 and 2 tankhouses capacity was increased by 15,000 metric tons per year to 138,000 metric tons per year.At present, the refining capacity is 258,000 metric tons per year in total including No.3 tankhouse.This figure is the largest one in Japan.IntroductionSince the Onaham tankhouse was put into operation in 1965, the cathode copper production has increase with much labor cost saving.The following two cases to increase Walker type anode copper weight by 35kg to 365kg were studied.a) To increase the cathode copper production by raising current density.b) To save the labor cost by prolonging the anode cycle in order to decrease the exchanging time of electrodes.So the electrolytic tests were carried out to confirm· the effect of current efficiency, cathode copper quality and working conditions for space adjustment.As a result, we concluded that it was indispensable to introduce the anode body press machine to keep usual current efficiency and cathode copper quality with same workers, and to be possible to increase cathode copper production.In addition, the high-speed press machine was needed to maintain same working time and which specifications were decided through various investigations. In October 1996, the new anode body press machine made by Kawazoe Machine Works, Ltd. has been installed in No.1 tankhouse."

Jan 1, 2000

By I. M. S. Moraes

Caraiba Metais has a plant for the purification and the cristallization of the crude nickel sulfate removed from its copper electrolyte purification system. In November 1994, an interdepartmental group was formed to study the Q.F.D. method, through its application on the improvement of the quality of the nickel sulphate hexahydrate. The team, formed with representatives of the following areas : production, technology, marketing, sales, maintenance, laboratory and TQC office, had also the task of checking the applicability of the method to other products of the comp any. This paper describes the main steps such as the survey of customer's demands, the preparation o1 the quality matrix, stablishing the planned quality matrix, the planned and the designed quality, and the consequent identification of the engineering bottlenecks. It is also shown how these bottllenecks were studied and solved. The application of the method allowed the team to identify means of increasing the production capacity by 40%, to improve the intrinsic quality of the product (including packaging), and to increase the reliability of the process.

Jan 1, 1997

By Jose Antonio Silva Souza, Emanuel Negrao Macedo, Iara Ferreira Santos, Otacilio Dias, Luis C. A. Venancio

"The Bayer process alumina production generates 0.7 to 2.0 ton of bauxite residue (BR) and an average of 1.0 ton of C02 per ton of alumina produced. The direct reaction of exhaust gases to reduce the alkalinity of the BR may allow a triple gain: improve the storage conditions, open a range of new applications for BR and sequester from 16 to 102 kg of C02 per ton of alumina. This paper shows the measurement of C02 captured during a pilot scale reaction of a suspension of BR in water with flue gas, produced from direct oil burning. Three different types of reactors were used: one spray tower and two packed columns. The inlet and exhaust gases were analyzed using electrochemical and non dispersive infrared sensors. The pH of the suspension was monitored during and after the reaction to evaluate the buffer effect.IntroductionAlumina is mainly produced from refining bauxite using the Bayer process. This process consists of extracting the aluminum oxide through its dissolution in caustic soda and the separation of insoluble residues. The remaining bauxite residue (BR) although not particularly toxic, poses risks to the environment due to the large volume and its reactivity. According to the latest technology it is stacked on sealed deposits specially constructed. To date the vast majority of the bauxite residue that has been produced was stored and were not incorporated into any existing production processes to significant amount with exception to some extent of the sintering process residue at Russia and China [l]. On the other hand, a strategic goal was set in 2010 by the Bauxite and Alumina Committee of the International Aluminium Institute (formed by the majority of the industries) to reuse 20% of BR in 2025 [2]. China has established the same objective for 2015[1].This paper is a sequel of two others presented at TMS 2010/2012 [3-4] and describes:• A pilot plant assembled for testing the carbonation process of BR with gaseous effluents similar of the refining process.• The methodology used to measure the amount of C02 captured during the carbonation process.• The results of the carbonation process, the C02 capture and the buffering effect of the pH.This process is studied in order to consume minimal power and use the effluent as efficiently as possible in different reactors from low cost to ultra high performance. The process is designed for minimizing the power consumption and equipment investment."

Jan 1, 2013

By T. A. Venugopalan

The 'Hall-Heroult' Process of reduction of Alumina to Aluminium has remainded basically the same for over 100 years, but the technology has been undergoing drastic changes with respect to selection of materials for Cathode and Anode, and also energy consumption. The latest generation pots have a working life of about 1800-2000 days normally. After the failure of the pots, the Cathode Lining is dug out and disposed of on land. Since the lining contains objectional materials causing pollution, various processes have been tried for re-processing of this waste. However, most of the processes have been unsuccessful from the techno-economic point of view. At Hindalco a new chemical process for converting the fluorine values of the dug out material to Cryolite was developed in 1988 and a" one ton per day Cryolite production plant has been operating since 1989. This process is especially applicable where the integrated Alumina and Smelter Plants exist side by side. The experience in operating this Plant is discussed in detail in the paper.

Jan 1, 1992

By Afshin Sadri

Acousto Ultrasonic-Echo (AU-E) is a technique developed to provide accurate measurements of the refractory lining wear in operating smelters based on the principles of stress wave propagation. The objective of the system is to provide feedback for the continuous optimization of the overall smelter operation. In some cases, the AU-E refractory lining measurements have allowed clients to extend their smelter campaigns and operate safely for several years beyond their planned reline schedule. In other cases, AU-E results inform clients of serious issues within their furnace allowing them to shut down their smelters ahead of predicted failures and possible disasters. This paper presents the results of several smelter AU-E inspections of the hearth and sidewall. These case studies demonstrate how the AU-E results were used to positively affect the smelter operation.

By Robert E. (Bob) Brown

Magnesium was discovered by Davy in 1808. The production processes as they exist are not economically competitive with aluminum The electrolytic magnesium process is divided into two steps; one to make the MgCh feed and the other to apply large amounts of electric current to dissociate the feed into magnesium (450 g) and chlorine (1200 g). The production of fuJIy anhydrous, pure cell feed is a major problem Recently, there has been a growth of thermal processes, mainly the Pidgeon silicothermic production process using FeSi to reduce dolomite in horizontal retorts. Pechiney has a large vertical electrical furnace process that also uses FeSi to reduce calcined dolomite in a molten bath containing alumina. Work is proceeding to develop new or modified processes that will greatly improve magnesium production. The present methods and the research and R&D will be reviewed in this paper.

Jan 1, 2001

By M. Kobayashi, Y. Nishisu

"Fine multicomponent particles of yttrium and europium were synthesized through the precipitation from homogeneous solution, and the various characteristics related with the fluorescence were investigated. The morphology and the fluorescent characteristics of the synthesized particles were affected by ionic species in the stock solution. In the presence of sulfate ion, some parts of the precipitated particles were aggregated, and _the fluorescent characteristics were not good. On the other hand, in the presence of chloride ion or nitrate ion, the particles precipitated were almost monodispersed, and, the intensity of the fluorescent emission were strong after calcination. Further, these particles were also very attractive as the red phosphor in the mercury-free fluorescent systems.Introduction Eu doped Y oxide particles have been widely investigated for the application to the fluorescent lamps and displays: Recently, the fluorescent lamps are pointed as harmful electric equipments because of using mercury for excitation. Therefore, the use of the mercury in the fluorescent- system will be limited or prohibited worldwide in near future. Then, the development of the mercury-free fluorescent lamp is strongly required without delay. Inert gas such as neon and/or xenon seem to be applicable as new excitation element that replaces the mercury. However, in case xenon the excitation wavelength,' 146 and 172nm, is different from that of the mercury, 254nm, and then, the commercial phosphors which are used in the present fluorescent lamp system are not available. Therefore, the invention of the novel phosphors is essential for the development of the mercury-free fluorescent lamp. Further, the controls of the size and shape of the particles precipitated are also important, because the homogeneity of the size and the shape is very important for the fabrication of the layer of the phosphor particles. That is to say, the development of the phosphor particles with controlled components, size and shape is essential. The precise control of size and shape improves the packing density, and so, the screen performance of the lamp [1]. In addition, these phosphor particles should be also useful for the application of the flat-plane displays, for example, PDP, etc. [2,3]. In the present work, first, the particles including yttrium and europium for the precursor for red phosphor were prepared through precipitation from homogeneous solution. This process was precisely controlled for the control of the components, size and shape of the particles precipitated. Next, the particles precipitated were calcined, and then, their fluorescent properties were characterized. As a result, some of them showed the possibly available characteristics as the red phosphor for mercury-free fluorescent lamp system. These experimental results are presented in this paper."

Jan 1, 2000

By Victor Zavodinsky, Sergey Rogov

"Pseudo-potential fully relaxed total energy calculations are used to predict a hypothetical Si1-xCxO2 (x<0.5) compound formed from SiO2 ß -cristobalite by substitution of some SiO2 complexes by CO2 molecules. The simulation shows that the Si1-xCxO2 compound can be quasi stable if the CO2 content is less than fifty per cent. It is assumed that six-molecule Si6-nCnO12 (n=3) rings can play a role of nucleuses for formation of the Si1-xCxO2 compound from SiO2 and CO2 molecules. Thus, silicon dioxide can be considered as a possible solid store for gaseous CO2.IntroductionThe problem of increasing of CO2 in the Earth atmosphere is one of the main modern problems of mankind. One of conceivable ways to decrease the harmful value of CO2 is to convert a part of it to solid state. Iota et al. [1] reported a polymeric (quartz-like) phase of CO2 solid synthesized at high pressure (~40 GPa) and at high temperature (~1800 K). Shortly after this experimental work, Serra et al. [2] reported a total energy calculation of several possible phases of CO2 using plane wave pseudo-potential density functional theory. They concluded that there should be a transition from a molecular phase to a phase isostructural to SiO2 -quartz in the range of 35 to 60 GPa. The latest calculations by Dong et al. [3] have shown that the more favored solid CO2 phase is ß -cristobalite. Recently, Kume et al. [4] have demonstrated the polymerization of CO2 even at room temperature at high pressures up to 80 GPa. Transformations of gaseous CO2 to different solid phases were studied recently experimentally and theoretically [5-8]. The main obstacle for using synthesized CO2 solid as a solution for the CO2 problem is its pressure instability. However the SiO2 ß -cristobalite with the same structure is stable.The question is whether a silicon-oxide system in which a part of atoms of silicon is replaced by atoms of carbon will be stable? If the answer is positive, this system can be considered, in our opinion, as a possible store for CO2."

Jan 1, 2009

By Adam Powell, Salvador Barriga, Matthew Earlam

"The inert anode is a key enabling technology for dramatic energy and emissions reduction in extractive metallurgy. In molten salts, the materials challenge is nearly insurmountable: the anode must conduct electrons at high temperature in a pure oxygen and molten salt environment. A solid electrolyte, e.g. zirconia, between the salt and anode removes the molten salt stability constraint, and can act as a container for a liquid metal anode. This can be liquid silver for oxygen-generating inert anodes, or several metals for natural gas-fueled anodes; it is possible to switch between these modes. The solid electrolyte brings several other benefits: it eliminates molten salt contamination of the anode gas, creates a reducing environment enabling low-cost steel vessels, increases current efficiency, and eliminates carbon contamination of the product. New developments presented here, including current collector and low-cost anode designs, amplify these benefits for producing aluminum, magnesium, rare-earths, and other metals.IntroductionReactive metals such as magnesium, aluminum and rare-earths play increasing roles in efficient transportation and clean energy. In response to new fuel economy standards, automotive OEMs are planning large increases in use of aluminum and magnesium to reduce vehicle weight. Rareearth permanent magnet motors and generators exhibit better power-to-weight and efficiency than induction motors and other designs, making this today's primary motor technology for hybrid and electric vehicles, and for wind turbines. Nickel metal hydride (NiMH) batteries with lanthanum are dominant in hybrids. In 2011, transportation comprised 28.6 out of 103.1 EJ of US energy consumption [1] and 1,845 out of 5,471 million metric tonnes (MMT = 109 kg) CO2e of US greenhouse gas (GHG) emissions [1], creating big targets for economy-wide reductions.Unfortunately processes for making reactive metals for these applications are very inefficient and heavily-polluting. In primary aluminum production, Hall-Heroult cell electricity use [2] is more than double the reaction enthalpy due to heat losses through frozen cryolite side-walls and anode gases, graphite anode plants add significant energy use and GHG emissions [2] (see Table 1). Magnesium is even worse: silicothermic reduction by the Pidgeon process in China produces about 85% of the world's magnesium using coal or coke gas [3]. Chloride electrolysis begins with high-purity MgO and requires carbochlorination or hydrochlorination and costly chloride dehydration [4]—rendered unnecessary for aluminum by the Hall-Heroult cell. Production of neodymium and lanthanum with graphite anodes leads to inconsistent carbon content: small cells make 1 kg batches for analysis, sorting and sale by carbon content, with very high labor and analysis costs. And vertical electrodes give no incentive to reduce anode effect: some reports indicate that China's rare-earth metal industry emits more CF4 and C2F6—with global warming potential (GWP) 6500 and 9200 times CO2 respectively—than China's aluminum industry [5]."

Jan 1, 2014

By Vladimir Mindin

Simulation of complex equilibria is usually done in the P-T-X coordinates, where "Xu is the amount of individual chemical components in the system. This approach is not productive in some very important cases: (i) investigation of "open" systems, (ii) determination of coordinates (trajectories) of mono-variant points, among others. To solve these and some other problems, we use the idea of chemical potentials of elements (CPE) of the system. A system of different coordinates axes (CPE-axes ) leads to a new strategy of simulation, observing the results of the simulation, and to efficient technology of compressing and storage the data of the simulation.

Jan 1, 1994

By Shadia J. Ikhmayies

SnO2:F/CdS:In bilayers were produced by the spray pyrolysis technique on glass substrates. The structures were characterized by recording and investigating their transmittance curves, I-V plots, X-ray difractograms (XRD) and by observing their scanning electron microscope (SEM) images. From the I-V plots it was found that the SnO2:F forms an ohmic or quasi-ohmic contact with CdS:In. XRD patterns show the polycrystalline nature of the films and show that there is a small shift in the position of the (200) line of SnO2:F without the appearance of new peaks. The morphology of the structures are compared with those of SnO2:F alone and CdS:In alone on glass substrates.

Jan 1, 2009

By I. Peerawattuk

Growing demand for Li-based battery technologies is leading to an unprecedented growth in the lithium industry. Although innovation in battery technologies has pushed lithium into the spotlight, lithium was not always known for its application in batteries. The primary use of lithium—prior to the introduction of commercial lithium-ion batteries in the early 2000s—was in the ceramics, glass, grease, and the medical industry. Before being converted into usable forms, lithium products must be upgraded from the raw material. Processes for recovering lithium may involve: thermal treatment, water leaching, solar evaporation, ion exchange, carbonation, and electrodialysis. Presented, is a historical review of lithium applications and the different techniques of converting lithium-rich minerals and brines into usable products with additional discussion on future lithium extraction processes.

By Junfu Chen, Jiann-Yang Hwang, Yong Zhou, Lijun Lu, Likun Lia, Jixiong Liu

The sheet-like NiS-ZnS heterostructured composites were prepared by the microwave hydrothermal. The fabrication of the heterojunctions broadened the range of light response of ZnS. The photoexcited electrons of ZnS migrated to the redox potential of NiS/Ni2S under visible light irradiation, which can facilitate the effective separation of photogenerated electrons and holes in space. The visible photocatalytic activity towards hydrogen production for NiS/ZnS nanosheet heterostructed composites without co-catalyst achieved 0.28 mmol h–1, and the quantum efficiency was up to 18.6% under the wavelength with 420 nm visible light irradiation.

Jan 1, 2015

By J. Brent Hiskey

Recently basic concepts of semiconductor electrochemistry and solid-state electronic structure theory have been applied to the dissolution of mineral electrodes. In this paper, fundamental aspects of semiconductor electro- chemistry and interfacial charge-transfer processes are reviewed. Information regarding the electronic and semiconductor properties of chalcopyrite is summarized. The electrochemical response of chalcopyrite in acidic solution is analyzed in terms of initial dissolution processes. The initial charge- transfer reaction involves the consumption of holes. It has been shorn that Fermi level pinning is consistent with observed electrochemical and dissolution behavior. Semiconductor electrochemistry has proved helpful in explaining the formation of intermediate surface films produced during the initial stages of chalcopyrite dissolution

Jan 1, 1993

By Tim J. A. Smith

Fundicion Refimet S.A. has operated a custom copper smelter at La Negra, near Antofagasta in northern Chile since 1993. From an initial operation based on Reverb smelting and Peirce-Smith, converting, the plant was expanded from 90 000 t/y to 160 000 t/y copper production in early 1997, by conversion to oxy-fuel smelting and use of concentrate injection on Converters. As part of this expansion a novel reverb gas cooling and cleaning system was developed and designed by Kilborn SNC-Lavalin Europe, the London, UK-based mining and metals; Office of Canada&apos;s SNC-Lavalin group. The reverb gas cooler needed to satisfy several very specific requirements including low cost, flexibility, robustness and simplicity of operation. Of particular importance was the requirement to cool and clean the ,oxy-fuel reverb gases and render them suitable for subsequent treatment in a conventional sulphuric acid plant. It was also important to avoid accretion or dust handling problems. This paper describes the key design features and subsequent successful installation, commissioning and operation of the unit.

Jan 1, 1998

By Jean Goldschmidt

Recycling of fine oxidized particles of non-ferrous metals usually cannot be carried out by pyrometallurgical methods. &apos;Hydrometallurgy provides an alternative technology to reintroduce? the resulting products as secondary raw materials into the industrial cycle, thereby saving resources and energy while keeping the environment a little cleaner. The paper summarizes the methods employed by Hydrometal to achieve these objectives and? stigmatizes the latest counterproductive international regulations which create ever more obstacles to environmentally sound recycling.

Jan 1, 1995

By Bien Ferrer

In most smelting operations, there is a strong incentive to improve safety, reduce downtime and extend the campaigns of furnaces and related equipment. An asset management strategy that is based on information, rather than simple throughput metrics and intuition, can be developed to improve uptime and unlock value currently unrealized at existing smelters. Advances in digital technology, including data analysis, modelling and monitoring for hot pyro-metallurgical vessels, make it possible to assess the current condition of an asset, as well as to make more informed projections about its future condition, using on-line and historical data. This would allow practices around asset management to be more proactive and less reactive, with the end-result of optimized uptime. ‘Digital Asset Management’ describes a concept in which digital technology is used to support an asset management strategy and accelerate decision-making by providing information on what, why and how an asset should be designed, operated or maintained. With the overall goals of effective resource utilization, optimized operations, capital efficiency and social acceptance, Smelter 4.0 is a program of holistic improvement and is underpinned by the effective use of data to drive decisions. This paper focuses on Asset Reliability, which is one of the improvement pillars of Smelter 4.0, and introduces a methodology that is aimed at closing the gap between recorded data and evidence-based decision-making through Digital Asset Management.

By P. Hanniala

In the day-to-day life the copper business of today is influenced directly by the ever-increasing general concern about the environment. In addition to that the inherent shortcomings of the copper smelting business, have since many years been the falling real price level of the metals and the relatively high initial capital investments required for the production units. These shortcomings have been compensated for by high productivity, low specific operating costs, low metal inventory and unbeatable technological superiority. Thus today more than 50 % of the world primary copper is today produced by utilizing Outokumpu Flash Smelting Technology. This figure is expected to grow at an increasing speed in the near future. Characteristic for the Outokumpu Flash Smelting technology is high flexibility for a wide grade of concentrates and the highest sulfur capture owing to at the same time competitive investment and operational costs. The Flash Converting technology offers new options for copper production and optimization of the mine- concentrator-smelter production chain. In the following years it is expected that the trend in copper making is that higher grade concentrates are produced at the mines. Thus increasing amount of high grade concentrate will be available for direct-to- blister Flash Smelting causing an overall cost reduction in copper smelting i.e. both in capital and operational costs. In the &apos;90s new technologies based on Outokumpu Flash Smelting technology have been taken into operation, thus eliminating the non-continuous Peirce-Smith converting process step. New innovative solutions have been used in the latest projects, as in Kennecott Utah Copper, where the new Kennecott-Outokumpu Flash Converting process was started up in 1995. Also, in 1995 the new DON process was started at Outokumpu Harjavalta nickel smelter followed by the Fortaleza nickel smelter in Brazil in 1997. The aim of the continuous development work at Outokumpu has been the expansion of the direct-to-blister process towards lower grade concentrates. The most recent example of this is the start-up at the Olympic Dam smelter in Australia, where the existing direct-to-blister Flash Smelting furnace was replaced with a new one having a capacity of 200 000 t blister copper per annum in just one smelting step.

Jan 1, 1999