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By Hidekazu Nakagawa

We investigated the anodic dissolution behavior of titanium in TMHA-Tf2N molten salt, which has a wide electrochemical window of about 5 V, in order to develop an electrodeposition method for titanium. By etching a titanium electrode in HF?HNO3?H3PO4 solution, the titanium electrode became electrochemically active, and a redox reaction was observed at around -0.15 V vs. I-/I3- in (TMHA-Tf2N)?HTf2N solution. We identified the redox reaction consists of the reduction of the proton and the oxidation of hydrogen. The diffusion coefficient of the proton in TMHA-Tf2N was calculated to be 6.9 10-8 cm2 s-1 at 50 °C from the cathodic peak current in the cyclic voltammogram. Anodic decomposition of the molten salt was not observed up to 6.0 V vs. I-/I3- on titanium electrode, while it was observed at around 2.0 V vs. I-/I3- on platinum and glassy carbon electrodes. Cathodic decomposition of the molten salt was observed at around -3.0 V on the titanium electrode, as well as on the platinum and glassy carbon electrode.

Jan 1, 2006

By Michael J. Nicol

Growing environmental and occupational safety concerns about the use of cyanide in gold processing has increased the interest in more acceptable alternatives. The most likely of these is thiosulfate. However, the thiosulfate process lacks a proven in-pulp method of recovering the dissolved gold, because activated carbon is not effective for the absorption of the gold thiosulfate complex .. Anion exchange resins do offer a possible route for in-pulp recovery. This paper describes work aimed at the evaluation of the effectiveness of commercially available anion exchange resins for the recovery of gold from thiosulfate leach liquors? and pulps. It has been found that strong-base resins are superior to weak-base resins in that they have a larger capacity, which assists in reducing the competition from other anions within a leach solution. Further studies with a selected commercial strong-base resin have shown that competing polythionateanions (particularly tri-and tetrathionate). Lower the maximum possible gold loading but that gold is selectively recovered over other base metal anions in solution. Kinetic experiments found that while? competilig anibns did not affect the initial rate? of gold loading it was important to minimise the contact time of the resin in solution so to prevent displacement of loaded gold by competing anions over longer times. A small-scale resin-in-pulp plant investigation showed gold can be recovered from a leach pulp by a strong-base resin to yield gold loadings of 3000 mg/L, barren pulp containing less than 0.05 mg/L of dissolved gold and. copper loadings of 500 mg/L. Loaded copper was displaced gold and at a loading of 2000 mg/L gold the copper loading was minimal «500 mg/L). The resin was found to recover gold adsorbed on the solids that would, otherwise have. reported to tails if a solid/liquid separation method were used. A patented two-step elution process in which copper and then gold are separately eluted from the resin is also discussed.

Jan 1, 1998

By Mike Dry

While McCabe-Thiele plots are useful for designing single-component solvent extraction systems, not least because of their simplicity, they are less useful for multi-component solvent extraction. This paper presents a relatively simple method, compared to other approaches, for modelling solvent extraction as chemical equilibrium reactions between the various aqueous and organic species. The essence of this approach is how values for the equilibrium constants can be extracted from standard laboratory data. Synergistic solvent extraction of nickel is used to illustrate the method.

By Nils Eivind Kamfjord, Mari K. Næss, Gabriella M. Tranell

"In oxidative ladle refining (OLR) of silicon, the metal surface is oxidized resulting in the formation of a condensed silica fume (SiO2). In the current work, industrial measurement campaigns were performed aiming to measure the fume generation during OLR. A thorough discussion of the possible mechanisms has been included in order to improve our understanding of the Si(1)-O2(g) system.The measurement campaigns were performed at the Elkem Salten plant in Norway. In addition to fume generation from OLR, the metal temperatures and ladle purge gas amount were recorded. The results of this work suggest that fume generation during OLR results from splashing of the metal and/or oxidation of the metal surface, with oxygen transport to the metal surface being the limiting factor. Other mechanisms of SiO2 formation were investigated, however insignificant.IntroductionOne of the main environmental and economical challenges facing the metallurgical industry is fugitive emissions of both materials and energy. In the production of metallurgical grade silicon (MG-Si), refining of the silicon generally takes place through an oxidative ladle treatment (purging with an air-O2 mixture). In the refining process, exposure of silicon to air results in the formation of condensed silica fumes (SiO2) – one of the main sources of fugitive emissions in silicon production plants. The oxidation of liquid silicon, as opposed to solid silicon, has not been widely studied and described in the literature [1], thus a thorough investigation of the oxidation mechanisms, and factors affecting the oxidation reaction rate are essential in order to deal with the problem. In the current work, the rate of liquid silicon oxidation has been studied through industrial measurements of fume generation from refining adles, where the purge gas rate and composition have been varied. The results from these measurements were discussed in light of existing models describing the liquid silicon oxidation kinetics."

Jan 1, 2011

By Guo Xueyi

The environmental impact assessment of the Imperial Smelting Process for metallic zinc and lead production in Shaoguan Smelter, China, was carried out by the life cycle assessment method. The detailed inventory analysis of the Input/Output in the process during 1998-2000 was conducted and the allocation was done among the main products of zinc, lead and sulfuric acid, according to the system expansion and substitution principle, The environmental impacts were assessed by using the following five Eco-indicators: Gross Energy Requirement (GER), Global Warming Potential (GWP), Acidification Potential (AP), Heavy Metal Toxicity (HMT) and Solid Waste Burden (SWB). The results from this study are useful to address the environmental situation of the technology practice in this smelter, and provide a scientific basis for the further improvement.

Jan 1, 2003

By E. A. Werner, A. Pichler, A. Spalek, G. Reisner, P. Stiaszny

"Interstitial free (IF) sheet steels are used for complex shaped parts because of their excellent formability. If a deep drawn part is subjected· to a impact deformation at low temperature brittle fracture of the part may occur. This phenomenon\ is called secondary work embrittlement (SWE). One possibility to characterize this material/structural behavior is the drop-weight test. The result of .this .test is a temperature at and below which a crack can initiated in a deep drawn part under the investigated set of parameters. This paper addresses the influence of the preforming process on the sus- . . ceptibili.ty of IF steels to SWE.IntroductionInterstiiial:free (IF-) steels are frequently used in the automotive industry for complex· shaped p·arts because of their excellent deep drawability. The microstructure of the steel consists of a highly ductile ferritic matrix with embedded precipitates of nitrides and/or carbides. Brittle fracture can occur in deep drawn parts, if they are subjected to a high speed deformation at lo""w temperature. This phenomenon is called ~econdary Work gmbrittlement (SWE) [1-11]. Up to now there are no standardized testing procedures available to quantify the sensibility of IF-sheet steel to SWE. Neveitheless, a reasonable testing procedure which allows to quantify the tendency of a predeformed part to SWE is necessary for further material development. A commonly used test method is the drop-weight test performed at low temperatures. In such ·tests a cone-like drop weight expands a deep drawn cylindrical cup [l-3, 6, 8, 9, 11]. From this expansion experiment the temperature is determined at and below which a brittle crack can be initiated in the deep drawn cup under the investigated impact test parameters. The highest measured temperature at which a deep drawn cup fails by brittle fracture is called frack appearances !emperature (CAPT). The lower the value of the CAPT the lower is the sensibility of a deep drawn part of IF-sheet steel to SWE. This paper aims to clarify the role of the preforming process on the impact behavior of an IF steel. For this purpose a numerical analysis of the deep drawing process and cup expansion tests are conducted."

Jan 1, 2000

By Alysson Tadeu Pereira Almeida

Steels with low concentrations of nitrogen, hydrogen and carbon have been in large demand lately. The RH process is a secondary refining process that can simultaneously attain significant levels of removal of these interstitial elements from liquid steel. In the RH process, the melt circulation rate plays a very important role in determining the productivity of the equipment, since it affects the decarburization rate. In the present work, a physical model of a RH degasser in a 1:5 scale of an industrial reactor has been built and used in the study of the circulation rate and of the kinetics of decarburization. The effects of the gas flow rate and of the configurations of the nozzles used in the injection of the gas have been analyzed. The decarburization reaction of liquid steel was simulated using a reaction involving CO2 and caustic solutions. The concentration of CO2 in the solution was evaluated using pH measurements. The experimental results indicated that the kinetics of decarburization can be described by a first order equation. Based on the results, it was possible to determine the contributions of the decarburization in the upleg snorkel and in the vacuum vessel.

Jan 1, 2006

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 Chu Yong Cheng

Synergists can be used in solvent extraction to improve the selectivity of extractants for metals. Research work carried out by the SX group at the AJ Parker Cooperative Research Centre for Hydrometallurgy / CSIRO Minerals has shown that the pH isotherm of nickel with Versatic 10 was significantly lowered by the addition of the synergist Acorga CLX50. The paper discusses how this synergistic shift can be used to alleviate a gypsum formation problem at Bulong nickel laterite operation in Western Australia. Metal pH isotherms were obtained with Versatic 10 and synergist CLX50 using synthetic leach solutions. In terms of pH50, the extraction order of the metals with 0.5 M Versatic 10 alone was Cu > Zn > Ni > Co > Mn > Ca > Mg, whilst the extraction order with Versatic 10 and 20% by volume CLX50 was Cu > Ni Zn > Co > Mn > Ca > Mg with the pH50 (Mn-Co) significantlyincreased. This is significant because the isotherms of valuable metals Ni, Cu, Co and Zn shift more towards low pH than those of the waste metals Mn, Mg and Ca, resulting in a possible good separation of Ni, Cu, Co and Zn from Mn, Mg and Ca. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel plants make these processes complicated and costly in capital and operation. The research work carried by the SX groupat the AJ Parker Centre has led to the development of direct SX (DSX) processes to recover nickel and cobalt from leach solutions using synergistic organic systems. Semi-continuous tests with a BHP Billiton pilot plant leach solution showed that Ni and Co together with Zn and Cu were separated from the major impurities, Mn, Mg, Ca, and Cl, in the first SX circuit. The co-extracted impurities were easily scrubbed. After stripping, Ni and Co together with Zn and Cu were concentrated, resulting in a much smaller second SX circuit in the down stream processes.

Jan 1, 2003

By Steven I. Baskin

Cyanides are utilized in many industrial applications including preparation of chemical intermediates, electroplating, and' mining, Cyanide has been utilized in chemical warfare operations as well Cyanide is also synthesized and found in plants and animals including man where it is thought to perform multiple functions. A variety of enzymes are known to detoxify cyanide under different conditions. These include rhodanese, 3-mercaptopyruvate-sulfur transferase, thiosulfate reductase, cystathionaseand albumin. Cyanide appears tQ exert its toxic effect primarily by inhibiting cytochrome oxidase? although other enzymes are also inhibited. Therapeutic antagonist categories to treat cyanide include methemoglobin formers such as nitrite, sulfane-sulfur donors such as thiosulfate, metal salts or complexes such as cobalt and cyanohydrin-forming compounds such as dihydroxyacetone or alpha keto-glutaric acid. Advantages and disadvantages of each category will be discussed. Newer compounds under development have been found that may allow for prophylactic therapy for cyanide poisoning with minimal side effects; In addition, portable co-oximetry devices may provide real-time measurement of cyanide in field units.

Jan 1, 1998

By William Petruk

The concentrator of the Iron Ore Company of Canada consists of spiral circuits, a cone plant and a magnetics plant with regrind. The proportions of liberated and unliberated grains of iron oxides at each point throughout the concentrator were measured by image analysis, and recoveries were calculated for each particle type by the MATBAL materials balancing program. The results show that spirals and cones recover more than 92% of the liberated iron oxide grains in the size range of 848 to 150 um,, but the recovery drops off rapidly for finer grained particles. The tailings from the spirals and cones are reground and low intensity magnetic separators are used to recover liberated magnetite in the -37.5 um size range. The concentrator does not have a unit that efficiently recovers iron oxide grains in the size range of 150 to 37.5 um Consequently about 25% of the iron oxides in the ore are lost to tailings as liberated. grains in the size range of 150 to 37.5 um

Jan 1, 1989

By Cynthia K. Belt

Improved energy efficiency has grown in importance within industry as energy costs have escalated. The analysis of trends and changes to a process is critical in making the best business decision in energy management. Frequently, energy use per day (Kilowatt-Hour or British Thermal Units) is used to track energy efficiency. Sometimes, the somewhat more complex method of energy per processed weight (Kilowatt-Hour per Metric Ton or BTU per Pound) is used to make this evaluation. Yet both methods ignore the effects due to throughput and weather. In this paper, different thermal processes and systems will be evaluated using statistical methods to highlight alternative methods to evaluate energy efficiency. Examples and potential problems will be discussed for both a single process and a collection of processes within a plant or corporation.

Jan 1, 2008

By M. J. Bagshaw, J. D. Hunt, R. M. Jordan

"Continuous casting processes, and the roll casting process in particular, offer considerable potential to the Aluminium industry, both meatallurgically and economically.The three major limiting process problems that occur during roll casting are Centre Line Segregation', 'Sticking' where metal adheres to the rolls during casting, and 'Heat Line' formation. 'Heat Lines' are localised semi-continuous longitudinal defects, usually a few cms in width, where the cast metal leaves the roll bite partially molten. These defects occur at relatively low casting speeds when the mean slab exit temperature remains several hundred degrees below the solidus temperature. The objective of the work described here is to develop a better understanding of the roll casting process in general, and in particular, to understand the phenomenon of 'Heat Line' formation.A steady state two dimensional finite difference model has been developed to describe the roll casting process, incorporating a variable heat transfer coefficient through the roll bite. In the model the difference equations are formulated using a control volume method and latent heat is incorporated according to the Scheil equation. A Gauss-Seidel type technique is used to obtain the solution. Because the rate of heat evolution is non-linear the temperature in each box is determined by using a Newton-Raphson method. The solution for a box can be multi valued and therefore lead to instability particularly near the vicinity of the front. A stability 'criterion is presented which shows that to obtain a stable solution it is better to have long narrow boxes rather than boxes with small dimensions in both directions.The model explains why heat lines form in terms of the variable slab/roll heat transfer coefficient.Experimental measurements of slab exit temperatures are also presented. These were obtained on a Hunter twin roll caster for the binary AI-Cu system, at two compositions over as wide a range· of casting speeds as possible. The experimental results are compared with the predicted ones."

Jan 1, 1986

By Dale W. Collins

The disposal of arsenic from copper operations possess various health, environmental and processing problems. There are basically two areas of concern. The first being the disposal or treatment of smelter flue dusts and the second the removal of arsenic from refinery electrolytes. A number of treatment options have been proposed including the addition of soluble arsenic wastes to copper heap and dump leaching solutions. This approach will allow arsenic to be reintroduced to the ore via Solvent Extraction (SX) raffinate associated with hydrometallurgical operations. Knowledge of the attenuation behavior and mechanism during leaching is important in determining the long term stability of arsenic and the success of this approach. Parameters, such as uptake capacity, pH, particle size and solution chemistry have been investigated. Arsenic attenuation has been examined using column leaching with experiments employing both continuous flow and pulsed additions of As(V). In the initial stages of leaching, the attenuation of arsenic appears to depend on the pH and iron concentration in the effluent. Arsenic stability in the copper oxide ore has been examined with rinses of progressively lower pH.

Jan 1, 1994

By Chris P. Pistorius

Over the past few decades the carbon intensity of ironmaking and steelmaking has been reduced considerably through improved efficiency in blast furnace ironmaking, partial replacement of coke with less carbon-intensive fuels, and increased use of scrap and direct-reduced iron in steelmaking. To evaluate possible further reductions in carbon intensity accurate process information is needed. A preliminary test of the fidelity of publicly reported data as a source of process information is reported here. The sources are industry roundups of electric furnace furnace steelmaking and blast furnace ironmaking (published by the Association for Iron and Steelmaking Technology), and data recorded by the Environmental Protection Agency under the US Greenhouse Gas Reporting Program. From a comparison for an integrated steelmaking plant and an electric furnace furnace plant, it appears that the values from the two data sources are consistent. The comparison does rely on process details such as the quantitative relationship between injected oxygen and carbon emissions in electric furnace steelmaking.

By Batric Pesic

A hydrometallurgical process for recovery of Zn and Mn from Bunker Hill Water Treatment Plant sludge was developed. The process is unique because it treats an unusual combination of metals, Zn and Mn. Another non-standard feature of the process is that leaching takes place with ~S04 in the presence of a reductant (SO2). Zn and Mn are recovered simultaneously by electrowinning, Zn on a cathode and Mn on an anode, as MnO2 The major purpose of the process is to detoxify the sludge by removing toxic heavy metals. The recovered metal values could be marketed to offset the overall costs of water and sludge processing. This work is presented in two separate parts, 1. Leaching and Solution Purification, and II. Electrowinning. This paper covers only the first part of the hydrometallurgical process: Leaching and Solution Purification. Initially, the paper briefly discusses the history of the pollution problem at the Bunker Hill Superfund Site, the origin of heavy metals in the mine waters, and the development and use of the water treatment plant. The leaching of sludge was examined as a function of the following parameters: constant vs. initial pH, initial vs. delayed addition of SO2, temperature, and pulp density. It was found that leaching with H2SO4 at pH 2.0 for 15 minutes (at 60°C), followed by S02 addition for another 15 minutes, could completely dissolve Zn and Mn. Solution purifIcation was done in three stages. In the first stage iron was removed by adjustment of pH (to pH 5.0) and oxidation offerrous to ferric iron (with H2O2). In the second stage, Cu and Cd were removed by Zn dust cementation. Finally, Co and Ni were precipitated with the organic reagents 1-2 nitroso-naphthol and nitroso, respectively. Electrowinning of Zn and Mn is discussed separately in Part II of this paper.

Jan 1, 1996

By Daniel Kittelty

A fully instrumented laboratory electrowinning cell has been used to produce nickel cathodes from synthetic solutions containing various impurities in order to evaluate the effects of both metallic ions and organic reagents (from prior solvent extraction and other processes) on the quality of the electrodeposited nickel. The conditions used were typical of those employed in industrial electrowinning operations. The impurities were found to alter the crystal size and shape, induce the development of hydrogen pits on the deposit surface, incorporate as metal hydroxide crystals in the deposit, and alter the internal stress and current efficiency. These effects have been interpreted in terms of previously established relationships between the solution composition and the physical properties of the cathodes. The incorporation of the common metal impurity ions into the deposit have been interpreted in terms of a mass transport controlled reduction or precipitation reactions. In particular, a low concentration of aluminium ions resulted in an initial highly deleterious effect, which was replaced by a positive influence at higher concentrations. A model which involves the buffering effect of the aluminium on the pH at the cathode surface has been proposed.

Jan 1, 2003

By B. Ozturk, K. Ito, R. J. Fruehan

"A simulation model for bath smelting processes for the production of iron was developed which predicts the coal, flux, ore, and oxygen consumptions and the off gas volume, temperature and composition. The model is comprehensive in that it takes into account all of the important variables including coal composition, metal composition, ore composition, slag basicity, post combustion ratio, (PCR), prereduction degree (PRO), heat transfer coefficient (HTC) , flux, scrap charge, and heat losses. Four basic cases were considered: I. 30% PRO-50% PCR; II. 90% PRO-O% PCR; III. 60% PRO-30% PCR; and IV. 0% PRO-50% PCR. Several different coals were considered and a sensitivity analysis of the critical variables was performed. The model also estimates the sulfur content of the metal. The major conclusions included:1. Post combustion significantly reduces coal consumption but above 20% PCR little reduction of FeO to Fe can be performed with the off gas.2. Prereducing to FeO (Case I) and having as much post combustion as consistent with good heat transfer is an attractive process. This process only requires a simple pre reducer, uses less coal, and is relatively insensitive to the type of coal used.3. High off gas temperatures may pose a potential problem. The off gas temperature can be reduced by using an 02-Air mixture for post combustion, limiting post combustion or adding water to the gas.4. The use of CaC03 in place of CaO or of supplemental electricity does not appear attractive.5. The melting unit is theoretically an energy efficient scrap melter. For Case I using 200 kg of scrap as part of the charge the coal consumption decreases by about 80 kg.6. With PCR > 30% the FeO content of the slag is expected to be 2-5%, and the metal will not be saturated with carbon. These factors and the increased sulfur load since coal is the fuel indicate the sulfur content of the metal may exceed 0.25%"

Jan 1, 1988

By John Petersen

Heap bioleaching technology has become well established for the exploitation of copper sulfide ores. Still, in many operations the rate of copper extraction is rather slow, often taking two years or more to recover 80% of the copper. Chalcocite, the most common secondary copper sulfide, leaches by a two-stage mechanism. The first stage is rapid, whereas the second stage has a high activation energy and proceeds slowly at ambient temperatures. Nonetheless, this rate is still considerably faster than what is typically realized in a full-scale heap. A comprehensive column bioleaching study of a chalcocite ore has shown that the chalcocite columns are leached in a zone-wise fashion. The first zone corresponds to the first stage of chalcocite leaching, where all ferric produced by the bacteria is immediately consumed and all acid entering with the feed solution is consumed within a relatively narrow band. The second stage of chalcocite leaching proceeds much more slowly in the wake of the first stage, within a zone that grows gradually over the entire length of the column. The overall rate of leaching is thus determined by the rate of acid supply into the column rather than by mineral or bacterial kinetics, at least until the entire column is engaged in second-stage chalcocite leaching. In full scale heaps, there is evidence to suggest that solution distribution favours channelling between relatively large clusters of material which are exposed only to stagnant solution. Reagents have to migrate into such clusters by diffusion, which retards the delivery of acid dramatically. Thus, we believe that the rate of chalcocite oxidation in heaps is governed by sideways diffusion rather than downward migration. Column experimental results have been reproduced with a comprehensive heap-modelling tool. The model predicts that by simply changing the length of the average diffusion channel from column conditions (a few cm) to heap conditions (tens of cm), extraction times can change from weeks to years under otherwise identical conditions.

Jan 1, 2003

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. The effects of feed matte grade, matte particle size, oxygen-to-matte mass ratio, oxygen content of the process gas and temperature on the particle oxidation rate, quality of conversion, particle size change and particle morphology were determined. The converting quality was highest (~68) with the 58% copper matte at 1100°C. At similar conditions, the 72% copper matte was more likely to produce copper oxides and leave unoxidized particles rather than directly produce sulfur dioxide at 1100°C, resulting in an average converting quality of 55. The quality of conversion was poorest for the 72% matte at 920°C (~45); the sulfur removal was extremely low even with a relatively high degree of oxidation. Fragmentation of the particles was significant in all cases with the 72% matte. A higher O2/matte .ratio and higher temperature, in general, resulted in increased fragmentation while oxygen enrichment had no significant effect. With the 58% matte, particle size was found to increase for the finest fractions rather than to decrease due to particle expansion.

Jan 1, 1998