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By Tabbetha A. Dobbins

We report studies concerning the time frame for catalytic reactions between NaAlH4 (sodium alanate) and TiCl3 during high energy milling. Spectral features in x-ray absorption spectra were analyzed for samples milled for various times (0 minutes, 1 minute, 5 minutes, 25 minutes, and 125 minutes). A structural transition from Ti3+ to Ti0 is observed within the first 5 minutes of milling. The Ti0 structure persists for samples milled for times longer than 5 minutes?even after those samples underwent a subsequent single hydrogen desorption/absorption cycle. Samples milled for less than 5 minutes retain Ti3+. For samples milled for 1 minute, the Ti-K edge position shifts from Ti3+ to Ti0 after a single desorption/absorption cycle. However, the first coordination sphere around the Ti0 absorber occurs at longer distances for 1 minute milled sample. These results hint at the formation of Ti0 pure metallic clusters upon desorption/adsorption cycling of 1 minute milled sample. Previously reported x-ray absorption spectroscopy studies have demonstrated the structural transition from Ti3+ (in TiCl3) to Ti0(determined to be TiAl3 found at the surface of the alanate powder). Aluminum deficiency on the NaAlH4 lattice is responsible for controlling hydrogen absorption capacity. These time-resolved spectroscopy studies suggest the possibility for controlling aluminum deficiency, while still maintaining titanium activation of the alanate powder, by manipulating the coordination environment of the titanium dopant during the first five minutes of high energy milling. Specifically, a possible approach to mitigating aluminum deficiency during doping would be to introduce an alternative species to which the to Ti3+ catalyst would form a metallic bond after the TiCl3 has attached at the surface of the sodium alanate powder and before the Ti3+ forms the TiAl3 intermetallic species.

Jan 1, 2006

By Xiang Ma, Halvor Dalaker, Kai Tang, Stefan Andersson

Silicon carbide (SiC) is one of the most important non-oxide ceramic materials for many industrial applications and is mainly synthesized by carbothermic reduction of silicon oxide by coke above 2200°C. Replacing natural gas (mostly methane, CH4) for coke in SiC synthesis could considerably reduce energy consumption and CO2-emissions owing to higher carbon activity of CH4 at lower temperature. The generally accepted reaction mechanism is that SiC is synthesized through gaseous intermediate silicon monoxide, SiO. In the present study, the reaction mechanism for the SiO and CH4 gaseous mixture has been examined using atomic scale modelling. Molecular dynamics (MD) using a reactive force field (ReaxFF) has been utilized to examine the initial stages of reactions involving a gas mixture of SiO and CH4 and surfaces of SiC. The MD results revealed some interesting SiC formation mechanisms. The reaction energies of the critical intermediate species were also estimated by density functional theory (DFT) calculations and the implications for the force field parameters used in ReaxFF was discussed.

Jan 1, 2015

By Sheng-hai Yang

The electrochemical synthesis was conducted in anhydrous ethanol solvent mixed with conductive reagent when tantalum plate was used as anode and stainless steel plate as cathode. The effects of different conductive reagents (such as NH4Br, (CH3)4NCl, (C4H9)4NCl), conductive reagent concentration and the space on the cell voltage and the current density were investigated. The current efficiency of electrosynthesis was more than 95%. The electrolyte, a mixed solution was then undergone air distillation and vacuum distillation to get the final product which was characterized by Fourier Transform Infrared(FTIR) spectroscopy, Raman spectra, 1H-Neclear Magnetic Resonance(1H-NMR) spectroscopy. Carbon and hydrogen contents in the product were determined by elemental analysis instrument. Results consistently show that the product was tantalum penta-ethoxide.

Jan 1, 2006

By F. Sanchez, A. Mejias, C. Frias, G. Diaz

"Crude zinc oxides are the major source of secondary zinc and are produced from fuming processes like Waelz kilns. The impurities of crude zinc oxides make difficult their processing in primary zinc refineries due to mainly high chloride tenor. Washing with sodium carbonate is a costly operation and chloride removal efficiency is not good enough, so further purification steps are required. The crude zinc oxides are easily treated using ZINCEX™ technology based on leaching, solvent extraction, and electrowinning. The ZINCEX™ process is commercially available and is designed to be a perfect barrier for metallic impurities and halogens, allowing selective zinc extraction in mixed chloride and sulfate leaching solutions. Other valuable components as lead and silver can be efficiently recovered from the leaching residue using PLINT technology in chloride media. Silver is recovered as silver cement and lead is precipitated as pure lead oxide or carbonate, which can be smelted at low temperature.IntroductionZinc is a fully recyclable metal and at present approximately 70% of the zinc produced worldwide comes from primary zinc while 30% originates from secondary materials. Nowadays, the zinc recycling rate is continuously increasing mainly through galvanized steel scrap processing, and crude zinc oxides are the major source of secondary zinc [1]. Secondary zinc oxides are obtained from fuming processes like W aelz Kiln, Rotary Hearth Furnace or Primus Furnace. Waelz is the dominant technology accounting for 80% of total crude zinc oxides production worldwide. In the Waelz process, steel dust is mixed with solid fuel reductant (coke breeze) and pelletized. It is then fed to the kiln and heated to a reaction temperature of l ,200°C. In such conditions, zinc, lead, and other non-ferrous metals are vaporized into the flue gas together with chlorides and alkaline metals. Mixed oxides are drawn from the kiln with the process gases and separated to produce typical crude zinc oxides [2]."

Jan 1, 2011

By Laurent Cohen

Since the 1970s, Solvent Extraction (SX) in hydrometallurgical processes has been a key enabling technology in the production of high-purity metals. Examples include copper, rare earth oxides, uranium, cobalt and nickel. Notwithstanding incremental improvements in extractant formulations, few breakthroughs can be recounted in this industry outside of the initial amine-, oxime- or phosphine-based reagent chemistries. However, the advent of lithium-ion batteries and their stringent requirements for critical materials (lithium, cobalt and nickel) offer new challenges and opportunities for SX. Solvay recently introduced a new extractant for lithium, CYANEX® 936, and developed unique modeling software capabilities in cobalt/nickel separation using CYANEX® 272, zinc SX using DEHPA® and rare earth separations using CYANEX® 572. This paper discusses trends in SX and provides insight on processing of critical materials essential to energy sources. It also summarizes the technical and economic benefits based on extractant selection and advances in modeling.

By Zdzislaw Miczkowski

At KGHM Polska Miedz S.A, a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass exchange inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed, The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ?The second zone moves slower into the grain and the rate of the movement is determined by the presence of oxygen, In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined, The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Lanre M. Oshinowo, André Bakker

"An understanding of the parameters that govern the just-suspended impeller speed, Njs, and the distribution of solids, is critical to the efficient operation of hydrometallurgical and other processes involving solid-liquid suspensions. In this paper, the distribution of solids in stirred tanks under a range of solids loadings (0.5 to 50 vol%) was predicted using CFD and validated against experimental data obtained from the literature. The multiphase flow is modeled using the Eulerian Granular Multiphase model. This paper will also review the established design parameter Njs in the context of scale-up and compare it to the quality of solids dispersion as a means of assessing correct scale-up in suspension tank design. The results of this study will describe a straightforward procedure to obtaining comprehensive information about reactor behavior with complex CFD models.The performance of hydrofoil impellers and a 45° pitched-blade turbine at suspending solids under different agitation speeds was studied. Both single and dual impeller operation have been evaluated. The settled solids fraction for speeds below N js, and the cloud height for impeller speeds above Njs were predicted. The CFD predictions are in good agreement with experimental literature data on velocity distribution and cloud height."

Jan 1, 2001

By Gregor Kücher

Lack of basic knowledge on the semi-direct recycling methods for hard metals hinders the application on an industrial scale. However, advantages like reduced expenses and lower environmental impact draw interest at future potentials. Consequently, this report aims to offer insight into the influence of varying bulky hard metal substrates during their lixiviation in acidic media with an oxidant. The statistical software Modde 11 assisted in the development of a design of experiments (DOE) for evaluation of the impact of average grain size, binder and tantalum carbide (TaC) content on the leaching characteristics. The other experimental parameters were constant. Among them were temperature, solution concentration and quantity, duration and substrate surface exposed to liquid volume. Eventually, prediction plots and factors of the computed model equation describe the effects of varying substrate qualities on leached binder metal and selectivity.

By Tam Tran

Most new gold mines in Australia are required to treat tailings to reduce cyanide levels before they are discharged to storage ponds to meet the stringent environmental management guidelines set by government statutory authorities. In New South Wales, the average level of weak acid dissociable cyanide allowed in open tailings dams is now limited to 20 ppm, As stringent environmental guidelines continue to be enforced in Australia as well as in other parts of the world, the management of cyanide wastes has emerged as a key issue for the gold mining industry. This paper provides a critical evaluation on technical aspects related to the use of ion exchange resins and affiliated processes in cyanide management and tailing treatment. Particular attention is given to the use of ion exchange resin technologies in the processing of mixed gold-copper ores, where cyanide usage is the highest. Information presented in this paper is heavily drawn from the experience on the application of ion exchange resin processes at May Day mine, in New South Wales, Australia and associated pilot plant test programs. Issues related to the management of thiocyanate, especially with respect to the recovery of cyanide from thiocyanate are also discussed.

Jan 1, 1998

By Liangying Wen, Xuewei Lv, Yuelin Qin, Feng Zhu, Guibao Qiu, Chenguang Bai, Meilong Hu, Shengfu Zhang

"The COREX process is the first reduction ironmaking technology with coal and pure oxygen to get high quality hot metal, which consumes a lot of high quality lump coal and some coke. In order to increase the utilization of fine coal, reduce coke consumption and enhance the competitiveness of the technology, the combustion behavior of pulverized coal injection in melter gasifier is studied experimentally. The results show that the combustion rate of PCI increases with the increase of temperature. And the combustion rate increases with decreasing coal particle size. Compared bituminous coal with anthracite, the former’s burning ratio is higher than the latter in the same granularity. The combustion effect is remarkable when coal blend of bituminous coal and anthracite with the smaller particle size is pulverized in COREX process.IntroductionThe COREX process is the first reduction ironmaking technology with raw coal and pure oxygen to get high quality hot metal, which consumes a lot of high quality lump coal [1-3]. However, the proportion of lump coal in raw coal is very small, and it is avoidless to produce fine coal because of mechanical coal cutter and storage and transportation process, so it is important to resolve utilization of fine coal in COREX ironmaking process in order to energy conservation and reduce the cost of hot metal [4]. Currently, Coal briquetting technology is adopted to utilization of fine coal in COREX process [5], but coal briquetting system has high investment cost and requires feasible adhesive agent. The pulverized coal injection (PCI) into a blast furnace is being used on a global scale to improve the stability and reduce the cost of blast furnace operations [6]. The successful development of PCI in blast furnace is contributed to pulverized coal in COREX melter gasifier. However, it is different in PCI process between COREX melter gasifier and blast furnace, and the differences are as follows: firstly, The air is injected into blast furnace, which temperature is about 1200 ?, but in COREX melter gasifier the normal temperature oxygen is blasted, so PCI in blast furnace begin burning in blowpipe, but the combustion of PCI in COREX melter gasifier is only in raceway. Secondly, the racway of COREX is smaller than that of blast furnace of the same size. So, the combustion behavior of PCI is complex in COREX melter gasifier, which is not use for reference."

Jan 1, 2012

By Von L. Richards

Rapid Freeze Prototyping (RFP) is a novel solid freeform fabrication technology that creates parts by depositing water droplets and freezing them rapidly to form layers. An investigation into the smallest thickness that can be achieved by the RFP process was conducted. The factors that could significantly affect the thickness of the part built by this process including substrate temperature, volumetric feed rate, table velocity, nozzle frequency, nozzle standoff distance, and head pressure were considered. A shell building technique for use with the RFP system has been developed. Thin wall ice patterns have been invested using production shell building techniques and an alcohol-based slurry. The finished shells were quantitatively evaluated by inspecting their total shell thickness, mold cavity dimensional reproducibility, and shell strength. Pattern loss is influenced by not only the alcohol / water interaction but also the starting thickness as it relates to thermal mass.

Jan 1, 2008

By Akira Yazawa

The continuous converting has attractive advantages, but further experimental studies on the slag are required, when the process is considered thermodynamically. The summarized experimental results, obtained with iron silicate slag and with ferrite slag and results relating to actual operation are described and discussed in this paper. At first, equilibrium relations at controlled oxygen potentials among three melts of silica-saturated iron silicate slag, white metal and copper are investigated. The results obtained for slag agreed with the thermo-dynamical predictions. Namely, to suppress a magnetite separation, the system should be at high temperature; in the case of the S02 gas of 10 kPa, for example, magnetite did not separate from the slag at 1300°C, but at 1250 and 1200°C the slag was saturated with magnetite even at lower SO2 pressure. Copper losses caused by dissolution of its oxide increased with increasing 5O2 pressure, and were slightly lower than those reported in previous papers without the matte phase. When the continuous converting slag does not contain any appreciable amount of silica - in contrast to the conventional smelting slag ferrite slag would form, but there was no published fundamental work on-ferrite slags. Hence, the melting behavior and activities of the system CaO-Cu2O-Fe2O3 have been investigated. The liquidus diagram in nitrogen atmosphere was, constructed using both thermal analysis and quenching method. The low liquidus temperature region without magnetite separation was found in the part of low content of Cu2O in the section Cu2O-CaO-Fe2O3 and Cu2O?Fe2O3¬CaO?Fe2O3. The activity of Cu2O in the system was also measured. Slags, composed-of CaO, Cu2O and Fe2O3, in platinum crucibles were equilibrated at 1250°C and controlled oxygen pressures. After quenching, the-composition of slag and platinum crucible were determined qualitatively. On the thermo-dynamic analysis of the results, iso-activity lines were drawn, and it was shown that the slag in the converting furnace of the Mitsubishi process exists in an adequate region of the composition triangle.

Jan 1, 1976

By Henry Hu

In high pressure die casting processes, proper control of temperature die yields a high casting production rate and superior quality components, Die temperature is usually influenced by various die design and process parameters such as size and location of intemal water cooling lines, flow rates of cooling lines, and pouring temperature of molten metal. Among them, the cooling water flow rate plays a major role in controlling thermal pattern of the die_ In order to develop an effective control strategy, data of local die temperature must be collected and analyzed, In this study, a PC-based data acquisition and control system (DACS) for die temperature control has been designed, and established, The developed DACS has three input channels for temperature signals and one input channel for water flow rate signals, as well as one output channel for a water pump, and is capable of displaying data in both curve format and value format. Implementation of the DACS in a laboratory setup has also been attempted, It should be pointed out that more advanced control mechanisms can be potentially integrated into this system in future,

Jan 1, 2003

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

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

Jan 1, 2014

By Mônica Suede Santos Silva

This work describes characterization of the performance of the tundish of a six strand continuous casting unit of the Companhia Siderurgica Belgo Mineira, Joao Monlevade, Brazil using physical modeling. Permanent and transient conditions, due to ladle metal composition changes are considered. Pulse and step tracer addition techniques are employed to assess the control variables. For transient conditions the degree of inter-mixing and the minimum residence time are determined with a view to optimize the process especially during the grade changes of steel.

Jan 1, 2003

By Ping Long, Bin Yang, Jian Wu, Xiumin Chen, Wenli Zhang

In this study, the analysis method of trace element in pure indium using glow discharge mass spectrometry (GD-MS) has been established by correcting the analysis result, which was obtained from non-standard quantitative method of GD-MS. The effect of instrument operating parameters, the resolution and isotopes and the pre-sputtering time on the determination results were investigated respectively. The optimized operating parameters of the instrument were obtained as follows: the discharge current was 37.5mA and discharge airflow was 475ml/min. Mass spectral interferences have been eliminated using selected resolution and isotope. The pre-sputtering time was 30 min. 4 trace elements in two pure samples were determined for 6 times. The RSD were less than 20%. The content of trace elements in indium samples was determined by GD-MS and Chemical Analysis Method of Indium which is tested by inductively coupled plasma atomic emission spectrometry, respectively. The results were consistent with each other.

Jan 1, 2016

By G. R. Waters

NMR360 is developing a suite of chloride-based metals extraction processes, with the first commercial operation scheduled for commissioning late in 2018. It is critical, therefore, that with the introduction of any new technology, that the circuits do not suffer from mechanical failures which will compromise the operation. Although chloride leaching is at atmospheric pressure and relatively low temperature, the main challenge is preventing corrosion, since the high proton activity makes even a small amount of acid behaves as though it were concentrated. An additional challenge in concentrated chloride circuits is the potential for solids precipitation. In this context, therefore, correct valve selection is crucial, and NMR360 has partnered with CGIS to ensure that the Severe Service Valves (SSVs) needed will perform over and above the definitions of the Manufacturers Standardization Society (MSS) of the Valve and Fittings Industry. This paper outlines what the minimum requirements are for SSVs in chloride leaching applications, drawing on five decades of industry experience from one of Canada’s leading valve experts.

By Zdzistaw MiGzkowski

At KGHM Polska Miedi S.A. a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass ex-change inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed. The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ? The second zone moves slower into the grain and the rate of the movement is deter-mined by the presence of oxygen. In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined. The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Christoph Sagadin

Corrosion mechanisms between high melting synthetic ferronickel slags and refractory were investigated. The used slags were prepared by mixing and melting of specific oxides. Substrates of the applied refractory material and specimens of FeNi slags were heated in a hot stage microscope up to 1650 °C. The experiments were performed under a defined gas atmosphere of 60% CO and 40% CO2. A further examination of the formed phases between slag and refractory occurred by scanning electron microscope. The investigations indicate that the slag penetrates between magnesia grains and partly dissolves magnesia. Spot analyses show that iron diffuses into the magnesia grains, which transform to magnesiawustite, meanwhile SiO2 forms different types of olivine like forsterite and monticellite. Thermodynamic calculations confirm the formation of these phases. The combination of practical lab scale experiments and thermodynamic calculations should finally contribute to an improvement of the refractory lifetime and performance.

By Colin Dessemond

Since 1950, the traditional process has been dominating the production of lithium compounds from spodumene ores to sustain the lithium market because of its economic viability and the markets need for technical grade (99.5% purity) product. This traditional process includes thermal conversion, acid roasting and lithium leaching. However, this process has not been challenged and very few studies have tried to explain its limitation (95% lithium yield) or optimize the thermal treatment. Here, α to β spodumene conversion and lithium extraction were performed in a rotary kiln on a 2 mm to 2 cm spodumene concentrate instead of a micrometric one using a 1050 °C, 30 min conversion treatment and 250 °C, 30 min, 30% H2SO4 excess leaching treatment. X-Ray Diffraction analyses were performed on the converted material to determine the conversion rate by Rietveld analysis. It was observed after thermal treatment that the α-spodumene particles fractured and divided while the impurities remained compact. A sifting was performed after thermal treatment and it was determined that 65% of the initial mass became finer than 180 μm. X-Ray diffraction analyses and lithium content measurement were performed on both fractions and it was determined that the finer fraction had a very high lithium content of 3.24 wt%. Lithium extractions were performed on both fractions separately. While the coarser fraction’s lithium yield was only 61% the finer fraction’s lithium yield went up to 99% without any additional treatment. These observations may open more economical ways for the traditional process by potentially bypassing two third of costly steps such as grinding.