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By Dave Tahija

"Many investigations are being performed with the goal of removing carbon dioxide from the atmosphere and permanently storing it in geologically stable settings. At the same time, carbon dioxide in the form of dissolved carbonate is steadily accumulating in the world's oceans. Both carbon dioxide sequestration and oceanic accumulation are constrained by the aqueous thermodynamics of the carbonate system. These constraints are illustrated using the STABCAL computer model to generate potential-pH and aqueous distribution diagrams of seawater in contact with various pressures of carbon dioxide gas. STABCAL diagrams and titration simulations are also used to model some potentially useful cation-carbonate sequestrationsystems.IntroductionAtmospheric carbon dioxide concentrations have risen dramatically in the past couple of centuries and are rising still, primarily as a result of human activities, especially the burning of fossil fuels. Increased atmospheric carbon dioxide concentrations have been implicated as a main cause of global warming but have other effects as well.Rising levels of atmospheric carbon dioxide result in increased concentrations of dissolved carbonate complexes in water, including the oceans. These dissolved carbonates interact with other dissolved substances, altering overall seawater chemistry, most noticeably causing lowered pH levels.Some of these chemical changes are observed directly, for instance the general drop in oceanic pH, [1], while others can be inferred and predicted using thermodynamic modeling. The chemistry of dissolved carbonate in seawater is not especially intricate, as such chemical systems go, but neither is it simple enough to be worked out on the back of an envelope. Interactions between the several simple carbonate species and all the major dissolved cations in seawater should be considered, as well as the effects of competing anions, especially chloride and sulphate, since they are much more abundant than carbonate in seawater."

Jan 1, 2011

By Florian Kongoli

"Lime ferrite" slag with limited silica content has proven to be a valuable choice in the modem processes of copper smelting and converting due to several advantages that this slag offers compared to classical silicate slags. Nevertheless the liquidus surface of this slag has been experimentally measured only at low oxygen potentials such as in equilibrium with iron or near it and in air. Although most of the smelting and converting processes that use this slag occur at intermediate oxygen potentials, the liquidus surface of this slag is not known at these conditions and the effect of oxygen potential and silica has not been correctly understood. This has brought some confusion in literature as well as in the industrial practice. In this work the liquidus surface of the calcium ferrite slags has been quantified by the means of a new thermophysicochemical model and a new type of liquidus surface diagrams which are very convenient for any industrial process that uses calcium ferrite slags. These diagrams can be easily used to select the lowest liquidus temperature of calcium ferrite slags at a minimum cost and can help design several fluxing strategies in copper smelting and converting processes. The effect of the oxygen potential and silica is also quantified and important industrially related conclusions are drawn.

Jan 1, 2003

By Shaohua Ju, Feng Jiang, Chuanhua Li, Jinhui Peng, Libo Zhang

A T-junction microchannel is proposed to overcome the existing problems in conventional solvent extraction of indium from zinc hydrometallurgical process. Experiments were performed to separate In3+, Fe3+ and Zn2+ from sulfate solutions using Di-(2-ethylhexyl)phosphoric acid (D2EHPA) as the extractant. The effect of parameters such as pH, microchannel size and contact time on the extraction behavior of In3+, Fe3+ and Zn2+ was investigated. At contact time of 2.52 s and initial solution pH of 0.48, the extraction efficiency of In3+, Fe3+ and Zn2+ was 99.13%, 8.31% and 2.45%, respectively and separation factor of In3+/Fe3+ and In3+/Zn2+ were almost 1229.54 and 4864.98, respectively. Then, the loaded organic phase was stripped in T-junction microchannel. At contact time of 33.6 s, 99.64% of stripping efficiency of In3+ and stripping equilibrium were reached, while concentration of Fe3+ and Zn2+ was lower than 0.01 g/L with good separation of In3+ from Fe3+ and Zn2+.

Jan 1, 2016

By V. Blet

Rare earth elements (REE) are regarded today as highly critical raw materials but currently lack suitable recycling processes. A combined hydro- and pyrometallurgical process aimed at REE recovery from used NdFeB permanent magnets was recently developed by the CEA. The process integrates the physico-chemical treatment of magnets, followed by a solvent extraction step for the recovery and intra-REE separation using a selective extractant. A subsequent pyrometallurgical treatment via molten chloride salt electrolysis allowed the isolation of pure Dy metal. Technical-economic assessment and life-cycle analysis were also conducted. Following this first successful demonstration, a new project aimed at the recovery of REE from end-of-life nickel-metal-hydride batteries is currently being developed in association with industrial and academic partners. The project aims at evaluating from an experimental and economic perspective different processes converging at the production of value-added products such as cermet materials for catalytic applications, purified REO concentrates, or metallic alloys.

By Pertti Koukkari

The novel Jarogain process combines treatment of the jarosite residue of zinc manufacturing and processing of arc furnace dust from steelmaking to a holistic recovery technology. The new hydrometallurgical approach is targeted to recover the major constituents (Fe, Zn, Pb) as well as valuable components such as Ag, Au, In and Ga from the jarosite-dust mixture as reusable concentrates. The fractionation process proposed by VTT and Aalto University takes advantage of jarosite being readily fine powder and directly available for wet chemical processing. Jarogain process provides an energy efficient opportunity for jarosite utilization as value added products. The experimental proof-of-concept of key stages of the process will be outlined with a comparison of available pyrometallurgical treatments of jarosite waste. The techno-economical assessment is based on estimated investment and variable production cost using the discounted cash flow (DCF) analysis.

By Batric Pesic

Calcium silicate slag (Di-Cal) and magnesium oxide condensate (MgO) are the by-products of magnesium smelting operations, As these oxides have acid neutralizing and metal precipitating properties, it was decided to examine their reactions with (a) individual heavy metals and (b) with a mixture of metals in solution, The resulting solid reaction products were further tested with respect to the stability of the contained metals, The stability of the solid precipitates were examined as a function of the method of precipitation and as function of the solution pH With respect to the method of precipitation, the performance of Di-Cal and MgO was compared to the performance of lime, an industry standard for heavy metal precipitation, Four different pH solutions (4,0, 5,0, 7,0 and 1 LO) were used to study the effect of pH on the stability of the precipitates. It was found that Di-Cal, in most cases, produced the most stable precipitates and thus, outperformed lime, Metal precipitates prepared by the addition of MgO were the most soluble for each metal studied, except for Se,

Jan 1, 2001

By Demaerel. J. P.

Arsenic plays a major role during electroreflning of copper. Both the arsenic content in the anode and the arsenic concentration of the electrolyte have, in conjunction with other impurities such as lead, antimony, bismuth and oxygen, a direct influence on the quality of the cathode. The mechanisms are currently slime. inclusion and precipitation of insoluble compounds in the bulk of the electrolyte. Arsenic has also been reported to have a depassivating effect on the anode. An influence on the anode slime adhesion has also been found. A literature survey is given and these data are compared with and completed by our own results based on lab and pilot scale experiments as well as on Olen tank.house practice.

Jan 1, 1987

By Andreas Orth

Outokumpu Lurgi Metallurgie has developed a process for the calcination and reduction of laterite nickel ore tines where the reduction of iron and nickel to the wustite/metallic states respectively, is performed in a fluidized bed reactor using reduction gas generated very cost effectively from natural gas in an autothermal catalytic reactor. As an option coal can be used as reductant as well as additional fuel. The process of reduction and calcination is very energy optimized. It uses the off gas from the fluidized bed reduction reactor, which still contains energy, to dry and calcine the nickel ore fines in a primary stage circulating fluidized bed (CFB) reactor. The product shows high metallisation of nickel and iron oxides reduced to the wustite stage. This results in considerable energy savings in smelting the prereduced product to ferro-nickel. Alternatively the product can be leached to produce nickel. Laboratory tests showed very high recovery of nickel and cobalt. Keywords: Fluidized Bed, Prereduction, Calcination, Ferro-Nickel

Jan 1, 2004

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 Takashi Araki

In this work, we have elucidated the two-step oxidative reaction mechanism of 2,4,5-trichlorophenol by adsorbing oxygen atom for oxidative decomposition reaction of 2,4,5-trichlorophenol on oxide catalyst surface using ab initio molecular orbital calculation. In the first oxidation, total energies of reaction products have been shown extremely stabilized at all oxidation positions. This reaction occurs due to charge transfer from benzene ring to adsorbing oxygen atom. As a result, ? bonding of benzene ring are weakened. However, the benzene ring of 2,4,5-trichlorophenol does not perform cleavage reaction. In the second oxidation, the benzene ring of 2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By N. B. Gray, I. F. Taylor

"Gas injection to promote chemical reactions or mixing is a feature of many metallurgical processes. Often the aim of gas injection is to bring about a chemical reaction between the gas and liquid but most of the past physical and mathematical modelling work has ignored the influence of such reactions. In the work reported here, cold model studies have been conducted in which gas reacts with the liquid into which it was injected. The rate of liquid mixing has been measured as an indication of the mechanical energy transfer. It has been found that gas generated chemically within the liquid is significantly less effective at promoting mixing than the equivalent volume of inert gas. The relative ineffectiveness of chemically produced gas is thought to be due to smaller bubble sizes in comparison to the inert gas case. Small bubbles characteristic of chemically generated gas move with low slip velocities relative to the liquid and lead to different turbulence generation mechanisms.IntroductionIn processes such as steelmaking, copper conversion, bath smelting and ladle steel finishing gas is injected into liquid metal where it reacts chemically or simply serves as a source of agitation. An understanding of fluid flow phenomena in such situations is an essential pre-requisite to the calculation of process intensity and the optimisation of vessel productivity. Traditional physical cold modelling approaches to prediction of liquid flow in such situations are now often augmented by the techniques of computational fluid dynamics. Even with the availability of numerical modelling techniques cold physical models continue to have an important role for validation because it is generally difficult to obtain quantitative data from high temperature processes.Almost all previous cold modelling work has been based on the injection of an inert gas into water or some other non-reactive liquid. Such models do not include the significant increase in gas volume inherent in some processes. For example the oxidation of carbon in steelmaking leads to a twofold increase in molar gas flux through the reaction:"

Jan 1, 1996

By Animesh Jha

The carbothermic reduction of chalcopyrite has been studied in the temperature range 1073 to 1273K in presence of lime. The role of lime during the reduction process is explained and the phase equilibria leading to the metallisation of copper and iron are discussed. The effect of coal and carbon monoxide on the reduction process have been studied and the rate governing steps are identified. This investigation also cites examples of possible mechanisms of physical separation of metallic Cu from iron during the reduction process.

Jan 1, 1992

By Takashi Araki

In this work, we have elucidated the two-step oxidative reaction mechanism of 2,4,5-trichlorophenol by adsorbing oxygen atom for oxidative decomposition reaction of 2,4,5-trichlorophenol on oxide catalyst surface using ab initio molecular orbital calculation. In the first oxidation, total energies of reaction products have been shown extremely stabilized at all oxidation positions. This reaction occurs due to charge transfer from benzene ring to adsorbing oxygen atom. As a result, 1£ bonding of benzene ring are weakened. However, the benzene ring of 2,4,5-trichlorophenol does not perform cleavage reaction. In the second oxidation, the benzene ring of2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By Forsén. O.

In this ?paper practical solidification of anodes containing nickel, arsenic, antimony and bismuth is compared with the equilibrium? diagrams and kinetic ?factors. In order to clarify the distribution of the impurity elements in the anode the structures were studied after the solidification and also after the electrolysis of anodes. This examination was carried out with optical microscope, scanning electron microscope and electrochemical measurements. All the nickel is remaining metallic in the copper matrix during the solidification and therefore nickel is dissolved in the electrolysis at all oxygen contents, when the nickel content is 0.25 wt-% or less in the anode. The practical .solidification mechanism of the anodes, when the nickel content exceeds 0.25 wt-%, proceeds by the crystallization of nickel oxides. In oxygen containing copper anodes nickel oxide is verified to crystallize together with antimony in certain conditions and to form a micaceous compound (3Cu2O?4NiO?Sb2O5), which may build up a very harmful floating slime in the electrolyte. Arsenic is strongly enriched along the phase boundaries in oxygen free copper anodes. An intermetallic compound Cu3As is formed when the amount of arsenic in the anode. exceeds 0.7 wt-%. This compound is more noble than the copper matrix. This means 'that a selective dissolution of copper-arsenic compounds takes place. The copper matrix dissolves more strongly than the grain boundaries. The solidification structures of oxygen free bismuth containing copper anodes show clearly the influence of bismuth. Thin bismuth films which are less .noble than the metallic copper matrix, are formed during the solid1ficatton process. As a result of this the?grain boundaries are dissolved faster than the copper matrix.

Jan 1, 1987

By T. M. Dreher

The difficulties associated with the operation of a classical rhodium refining process have prompted many attempts to develop a viable solvent extraction flowsheet for rhodium. Recent investigations at McGill University have involved the activation of rhodium prior to its solvent extraction. The role of activation is to convert the aquochloro complexes of rhodium to a form extractable by conventional solvent extraction reagents. In the novel separation scheme identified, chloro complexes of rhodium are converted to bromo complexes, which undergo aquation to a lesser extent, making them more easily extracted. Rhodium is then extracted using Kelex 100, and stripping is achieved by use of a concentrated chloride based solution. Separation of rhodium from iridium is achieved by either prior reduction of Ir(IV) to Ir(III), as the latter is not extracted, or via co-extraction and differential stripping. A conceptual flowsheet for the refining of rhodium using this method is proposed.

Jan 1, 1998

By R. David Prengaman

During the past several years a new insoluble lead anode has been developed for copper electrowinning. The new anode consists of a rolled lead-calcium-tin alloy sheet attached to a slotted copper bus bar by a soldering process which produces a complete metallurgical bond between bar and sheet. The metallurgical bond greatly reduces the resistance between the bus bar and the lead sheet and the high conductivity does not deteriorate during the life of the anode. The rolled anode thins uniformly and does not suffer preferential grain boundary or internal corrosion commonly seen in cast anodes. The lead-calcium alloy containing a high tin content corrodes slowly because the rolling process produces a uniform, fine grained structure. The wrought product is very strong and ductile; and contains no internal defects, segregation, cracks, or pores which can reduce the life of the anode. Because the anodes corrode uniformly, a high percentage of the anode thickness can be utilized thus extending the life of the wrought anodes. The anode alloy composition which is stable only in wrought form, produces exceptional resistance to passivation during current interruptions. First introduced into liberator cells, the new electrowinning anodes have been specified as the anodes of choice for every new SX-EW tankhouse constructed in the last two years. This paper describes the new anode, its method of construction, service history, and how it differs from present copper electrowinning anodes.

Jan 1, 1987

By Cassandre Nowicki, Louis Gosselin, Carl Duchesne

"Quebec's primary aluminium production industry consumes roughly 39 TWh of electricity per year and is accountable for roughly 7 million tons of CO2 equivalent. By tapping only a small portion of waste heat and integrating it inside the production facility itself, we can significantly reduce GHG emissions and energy consumption. Although the amount of thermal waste can be adequately estimated by applying an energy balance to production processes, this provides very little information on the quality of waste heat and its potential for integration. A measure of exergy is required. Waste heat streams characterized by high exergy content may generally offer valuable incentives for recovery and integration. More generally, exergy values limit integration possibilities. An exergy analysis is provided for the aluminium electrolytic reduction process. This is meant to guide future heat recovery initiatives and energy efficiency measures.IntroductionCanada is one of the world leaders in primary aluminium production and 92% of its aluminium production capacities are located in the province of Quebec. In 2007, production capacity reached 2,786,000 tons in Quebec alone. Since it is estimated that 2.5 equivalent tons ofCO2 are released for each ton of aluminium produced in Canada, Quebec's aluminium production industry is accountable for roughly 7 million tons of CO2 yearly [1, 2]. Furthermore, with an average electricity consumption of 14 MWh per ton, primary aluminium accounts for 39 TWh of electricity per year in Quebec and this energy consumption represents 350 thousand tons ofCO2 equivalent [3, 4]. Natural gas consumption associated with primary aluminium production accounts for less than 1 TWh, but it represents an additional 350 thousand tons of CO2 equivalent [ 4].This work is meant to provide a tool to guide future efforts towards heat recovery and energy efficiency in the primary aluminium industry. Waste heat recovery and thermal integration can cut down both energy consumption costs and GHG emissions. In a primary aluminium production facility, waste heat represents roughly half of the energy input into the Hall-Heroult process. Tapping only a small portion of this energy could reduce natural gas and electricity consumption significantly. In order to evaluate how much of this energy is actually usable, we propose to apply an exergy analysis to individual transformation processes in an aluminium production facility, such that a potential to do work can be assigned to every waste heat flux. The approach will be described in the next section."

Jan 1, 2012

By C. Beckennann, C. Y. Wang

"Computer simulations of structural and compositional development in equiaxed dendritic alloy solidification are performed using a recently developed multi phase model. The model not only accounts for the transport phenomena occurring on the macroscopic (system) scale, but includes also the grain nucleation and growth mechanisms taking place at various microscopic length scales. In this paper, a numerical technique consisting of a fully implicit control-volume based finite difference method and a multiple time step scheme is developed for accurate and efficient simulations of both micro- and macro-phenomena. Sample numerical results are presented to reveal the effects of liquid now and crystal sedimentation on segregation and the final grain size distribution. In particular, the importance of the interplay between the dendrite microstructure and multiphase now patterns is shown.IntroductionIn recent years, modeling of equiaxed dendritic solidification without convection has experienced considerable progress (1,2]. Nucleation and growth kinetic laws have been coupled with transient heat conduction calculations to determine the solidification microstructure. However, modeling of equiaxed dendritic solidification with melt convection and solid movement has not been attempted so far, largely because of the complications associated with the transport of free equiaxed crystals in the melt. The gravity-induced transport of free crystals is fundamental to the development and extent of the equiaxed zone and also greatly affects the columnar to equiaxed transition. Another possible effect of crystal sedimentation or floatation is to cause severe macrosegregation as well as structural inhomogeneities. The only study available in the literature that accounts for both liquid convection and solid transport is by Ni and Beckermann (3], but deals with globulitic structures (as opposed to dendritic)"

Jan 1, 1994

By Peter Stiaszny, Andrej Samoilov, Yuri Titovets, Gottfried Hribernig, Nikolai Zolotorevskii

"The model has been developed to simultaneously predict both transformation product portions and mean ferrite grain size from the same common · principles as a result of the austenite decomposition during any cooling path of dual phase steels. The transformation products considered are polygonal ferrite, pearlite, bainite and martensite. The model is based on the classical equations of nucleation-growth theory and also contains some empirical parameters. The chemical driving forces for nucleation and composition of elements at the phase interfaces are derived by computation thermodynamics. The empirical parameters related to the model were determined on the basis of a series of austenite transformation dilatometric curves and grain size measurements for continuous and interrupted cooling of several steel types. The model is aimed to predict phase transformation in the complex cooling conditions of the run-out table of the hot strip mill at YOEST-ALPINE STAHL LINZ GmbH as a part of the computer aided system for prediction and on-line controlling of the mechanical properties of hot-rolled strip.IntroductionThe term ""dual phase steels"" is used to refer to a steel consisting essentially of a dispersion of martensite in a fine-grained ferrite matrix. These steels are of increasing technological interest since they provide a better combination of strength and ductility than any other conventional steel sheet material. The strength is important because it offers an opportunity to produce lighter components, while good ductility is needed to permit easy forming of components. It is generally recognized that martensite plays an important role in determining the strength level of dual phase steels. A full understanding of the role played by the phases in determining such characteristics requires investigating in more detail how to optimize the martensite level of such steels, while maintaining good ductility remains the subject of continued research in the industry."

Jan 1, 2000

By Marc Verhaege

The effluent under investigation results from a catalic oxidation unit in which paraxylene is oxydised to terephtalic acid. The solution contains cobalt and manganese as their acetates in a concentration range of 0,4 - 1,2 g/I of cobalt and 0,8 - 2,4 g/l of manganese. Before being fed into the main waste stream treatment unit of the plant it is advisable to apply a petreatment step in which both metals are eliminated to a great extent from this effluent. Conventional treatment is done by precipitation of both metals either through pH increment with a base or by adding a suitable reagent producing insoluble species. The aim of this study was to look for a treatment (elimination of both metal species) in which no sludge or precipitate is formed.

Jan 1, 1995