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By M. Neises, M. Roeb, C. Sattler, S. Stenger

"A two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split carbon dioxide as well as water molecules by extracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source, a promising method exists to produce synthesis gas from water and CO2. An easy way of operation is gained by the combination of a ceramic substrate as the absorber structure, which can be heated to high temperatures with concentrated solar radiation, and of a metal oxide coating which is capable to carry out the redox reactions. The performance and kinetics of a ferrite based redox material coated on ceramic substrates were investigated in a laboratory set-up. CO2 could be reduced with significant conversions. In addition, several side reactions were observed like the formation of carbon and like the Boudouard reaction.IntroductionThe search for alternative energy carriers and for processes able to reuse carbon dioxide stimulates the research for sustainable routes of alternative fuel production. In the scope of this search thermo-chemical processes combined with sources of concentrated solar energy have become more and more attractive. Ideally, the only raw materials for such processes are water (H2O) and carbon dioxide (CO2) enabling not only a process free of emissions, but also allow to reduce emissions of other processes by reusing CO2 to provide synthesis gas, which itself can be applied to produce chemical commodities or even better synthetic fuels like methanol or petrol.In contrast to the direct splitting of those raw materials, thermochemical cycles split water and CO2 in several steps and enable hydrogen (H2) and carbon monoxide (CO) generation at temperatures controllable by today’s technical equipment. One of the most interesting thermochemical cycles is a two-step process using metal oxide based redox systems. During the first step of this cycle (the regeneration step) the metal oxide is reduced setting some of its lattice oxygen free according to reaction (1). In the next step (the splitting) the reduced and activated material is oxidised by withdrawing oxygen from water and CO2 and at the same time hydrogen and CO is set free according to reactions (2a) and (2b) respectively."

Jan 1, 2011

By C. -S. Jiang

In most copper refineries, addition agents are added at predetermined rates with no further monitoring of their activity or concentration in the electrolyte. Increasingly stringent cathode quality requirements, and a desire for better process control in tankhouse operations, have recently directed a number of refineries to search for a better addition agent control strategy. Extensive development work has been carried out at the Noranda Technology Centre for the monitor in of glue and thiourea in copper refinery electrolyte using cyclic voltammetry (cv~. Data from both synthetrc and commercial electrolytes are presented, showing the ability of CV to produce reliable and easily identifiable fingerprints of addition agent concentrations in copper refinery electrolyte.

Jan 1, 1991

By Gavin Beer

The Chelopech Copper/Gold Mine, located in west-central Bulgaria, has been in operation since 1953 producing a low-grade copper/gold concentrate containing up to six percent arsenic by weight. The penalties and restrictions imposed on smelting this concentrate, have seen the past operators of the mine strive to find a balance between achieving acceptable metal returns from the smelters and installing novel or unproven technologies in the face of changing political and economic climates. This paper documents the colourful history of the concentrate processing alternatives that have been investigated and implemented over the 45 year life of the Chelopech Mine, culminating in the high pressure oxidation option that is now the focus of a Definitive Feasibility Study (DFS) presently being undertaken by GRD Minproc Limited. The fundamental chemistry of the preceding alternatives is outlined followed by a discussion as to why each was ultimately not employed. A detailed description of the technology proposed in the DFS is given including: pressure oxidation, arsenic fixation, SX/EW copper recovery, CIL gold recovery and AVR/SART cyanide/copper recovery processes. Keywords: Arsenic, Scorodite, HPOX, Chelopech, Dundee

Jan 1, 2005

By Timothy W. Ellis

"This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process scheme is discussed and a detailed description of several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this method to separate rare earth and other metal based materials will be given.IntroductionConcerns over the effects of waste materials in the environment has been one of the significant social hallmarks of the late 20th century. Essentially every industrialized country has had to incorporate the cost of waste material into the equation of production. Legislative initiatives have led to the passing of very tough laws, by historical standards, which govern the environmental impact of materials processing.Liquid-Liquid extraction is a very common unit operation normally using aqueous and/or organic based solvents. Early work at the Ames Laboratory focused on the use of this technique for the reprocessing of spent fuel from liquid metal breeder reactors by the use of metallic solvents. Recently, we have revisited this area as a means to recycle/reprocess several emerging rare earth based materials, although this method has a much wider range of application. The reinvestigation of this technology is particularly timely as hydrometallurgical based processes are coming under increasing scrutiny in the U.S.A. by the Environmental Protection Agency (EPA). Although technology currently exists to remove contaminants from aqueous based waste streams, often the application of such methods is expensive. With proper design and judicious selection of reagents liquid metal extraction can achieve a high recovery along with a benign waste stream.This process has several possible advantages over other technologies. First is the elimination of aqueous solvents. Therefore, problems associated with disposal or reprocessing of the aqueous carrier are eliminated. Second, with proper system design, very high separation coefficients can be obtained thus limiting the number of stages required. Third, metals are extracted from metals with a metallic product, thereby eliminating the need to re-reduce metal for oxides or other compounds which are the common output for aqueous based extraction procedures."

Jan 1, 1996

By J. B. See

Emeritus Professor David Robertson of the Missouri University of Science and Technology was born in Dublin Ireland on 29 December 1941. His father was a merchant navy Captain who served during WWII and during David’s early years his family lived in Dublin and Donegal where David went to the local elementary school. In 1954 he moved to London with his parents and attended Highgate School before commencing metallurgy at the Royal School of Mines, Imperial College, London in 1960.

Jan 1, 2014

By M. K. Yelloji Roa

Effect of conditioning with Thiobacillus ferrooxidans on the floatability of sphaierite and galena has been determined in this work. The flotation behavior of the conditioned minerals clearly shows that such bacterial conditioning does produce marked modification of their surfaces. The variables affecting the surface modification and thereby the flotation response of the minerals were found to be cell concentration used for bacterial conditioning, the period of biotreatment and the pulp density. Importantly, while the enhancement in flotation obtained due to sulphuric acid treatment was retarded by biotreatment in the case of galena at all cell concentrations due to electrochemical effects, such decrease occurred in the case of sphalerite only at cell concentration sufficiently high for their attachment to the mineral surface. The effect of bacterial conditioning has significant implications to the differential flotation of sphalerite and galena. Mechanisms responsible for the modification of the surface properties of these sulphides due, to bacterial conditioning are discussed.

Jan 1, 1991

Rotary kiln incinerators are widely used in the incineration of various types of hazardous wastes. However, the complex transport processes within the incinerator are not well understood. Due to large variations in waste types and difficulties in feed characterization, the incineration process meets great challenges in a smooth operation, and expects uncertainties in the process chemistry and emission control. In order to get better understanding of the incineration process, process simulation was made on the kiln behavior by using Computational Fluid-dynamics (CFD) to characterize gas flow, temperature distribution and waste combustion in the incinerator. Temperature measurement was conducted in an operating incinerator to validate the CFD model. This paper addresses the environmental issues related to the hazardous incineration process, and reports the recent simulation results on gas flow and mixing, combustion heat transfer, and potentials to reduce emissions.

Jan 1, 2002

By Bora Derin

The synthesis of titanium diboride (TiB2) by carbothermal reductions of TiO2 and B2O3 was investigated. For this aim, TiO2, B2O3 and carbon black powders were dried, weighed out and mixed in stoichiometric molar proportions (TiO2:B2O3:C = 1:1:5). The experiments were carried out in a graphite resistance furnace in argon media using different range of temperature (1400- 1700 °C) and time (0 and 15 min). The phase analyses observation of the products were examined by using XRD.

Jan 1, 2008

By Jan Yaozhong

The composition and the possible utilization of Ti bearing blast furnace from a titanomagnetite blast furnace smelter were studied. The slag contained about 20% Ti02 and trace Sc. The mineralogical analysis indicated that Ti in the slag is mainly as perovskite. By means of magnetite separation, the Ti containing phase could not be enriched. An effective hydrometallurgical approach was proposed with sulphuric acid leaching. The method proposed for processing the studied slag renders product Ti02 and SC203. Besides the recovery ofTiO2 and SC2O3' the leaching process yields fine grained residues which can used as additives for making cement.

Jan 1, 1996

By V. D. Tathavadkar

Natural chromite mineral is a solid solution of spinet end members namely: chromite (FeCr2O4), hercynite (FeA1204), magnetite (Fe3O4), magnesio-chromite (MgCr2O4), (MgA12O4), and magnesio-ferrite (MgFe2O4). A phase transformation in chromite minerals occurs in oxidising conditions during the soda-ash roasting reaction. This phase transformation plays an important role in improving the extraction efficiency of Cr3+ from mineral phase. The extraction efficiency of chromium (Cr3+) from chromite to a water¬soluble sodium chromate (Cr6+) salt depends upon the decomposition kinetics of the spinet phase. An investigation of the phase changes in chromite ores in the absence of sodium carbonate was carried out in air, argon, and in argon +5 % hydrogen gas mixture. The thermodynamics of phase transformation reaction in chromite solid solution phase is discussed using the solution model proposed by Sack and Ghiorso [1]. The microstructural changes and the changes in elemental compositions of different phases were examined by SEM and electron probe microanalysis (EPMA) respectively. The experimental results indicate that the solid solution spinet phase in chromite mineral undergoes spinodal decomposition under the influence of oxygen partial pressure and temperatures. The structure of phases formed and their morphologies suggest that the phase decomposition may be similar to those observed by Burkert et. a]. 121, although the scale of phase separation in chromite appears to be strongly dependent on oxygen partial pressure.

Jan 1, 2001

By Dajian Wang

To obtain the thermodynamic properties of a multicomponent liquid alloy system over the whole range of concentration at an arbitrary temperature, the free volume cell theory has been applied to derive the formula of activity coefficients of liquid solutions based on the infinitely dilute solutions at some temperature. The linear logarithmic relationship between activity coefficients of binary dilute solutions and reciprocal of absolute temperature have been verified, and are in good agreement with the experimental values from the literature. The Monte-Carlo algorithm was used to calculate the nonlinear end value equations of binary systems, then the free volume parameters obtained were correlated with the activity coefficients of liquid binary, ternary, and quaternary systems at an arbitrary temperature. Three dimensional a-X-T diagrams of some binary systems representing the temperature and concentration dependence of activities were plotted. The calculated results regarding non-ferrous alloy systems have been statistically examined with the experimental values from the literature. Hence, this simple approach could be useful for analyzing thermodynamic properties of liquid alloy systems.

Jan 1, 2000

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FeAsyO2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS2O3 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Jacques Magnaudet, Julie Cranga, Didier Huin, Pascal Gardin

"With the aim of controlling steel grade in steelmaking reactors, IRSID and IMFT are developing a numerical description of the evolution of bubbles in the vicinity of a liquid steel/ slag interface. The objective is to identify the main parameters affecting the hydrodynamics of the various phases. The goals of the present paper are:• To describe the numerical technique developed to predict the multi phase flow including bubbles, liquid metal and slag layer.• To analyze the influence of the absolute pressure on the bursting of bubbles in a RH degasser. Validation is given by comparison with results available in the literature. The major point concerns the distinct behaviors observed whether the pressure is low or high.• To study the influence of the properties of the slag layer (thickness, viscosity and interfacial tension) on the entrainment of liquid metal in the wake of the bubble and on the nature of the projections from the bath surface.IntroductionMost of secondary steelmaking processes use gas stirring for homogenization, removal of nonmetallic inclusions or decarburization under reduced pressure. The bursting of gas bubbles at the metal or slag layer surface produces a beneficial ejection of metal droplets in the low pressure atmosphere, provided that there is no violent projection, which may have detrimental effects on the process.Our objective is to develop a numerical tool to study the phenomena occurring in the vicinity of the bath surface, in particular bubble bursting under reduced pressure and entrainment of metal in the slag layer. In this paper we report the first conclusions of our study. In the first section we describe the numerical model used to describe the three-phase flow and the expansion of the gas bubbles under the effect of the ferrostatic pressure. The second section is devoted to the study of pressure effects on bubble rise and bursting. The third section reports some computational results about the rise of a gas bubble through the interface between the two liquids."

Jan 1, 2001

By Chu Yong Cheng

The solvent extraction (SX) processes of the three pressure acid leach (PAL) nickel plants in Western Australia have been reviewed. The use of intermediate precipitation, solids/liquid separation and re-leach in the three W A nickel plants make these processes complicated and costly in capital and ?operation. The research work carried out by the SX group at the AJ Parker Cooperative Research Centre for Hydrometallurgy I CSIRO Minerals has led to the development of direct solvent extraction (DSX) processes to recover and purify nickel and cobalt from leach solutions. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new DSX processes over the reviewed processes. By using a new synergistic organic system in semi-continuous tests with a pilot plant leach solution (after iron precipitation) from BHP-BiIliton Stainless Steel Materials, the metal values (Ni and Co) together with zinc and copper were separated from the major impurities (Mn, Mg and Ca, together with Cl) in the first SX circuit. The co-extracted manganese, magnesium and' calcium were easily scrubbed out. After stripping, the metal values (Ni and Co) together with zinc and copper were concentrated, resulting in a much smaller second SX circuit and equipment in the down stream processes. The extraction and stripping kinetics of the metals with the new synergistic organic solution were very fast. The extraction and stripping almost reached steady state within 0.5 minutes. Semi-continuous test work with a synthetic leach solution, a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton Stainless Steel Materials showed that manganese, calcium, copper and zinc can be effectively and efficiently separated from nickel, cobalt and magnesium by extraction, scrubbing and stripping. This led to the development of another DSX process using D2EHPA to recover nickel and cobalt from leach solutions.

Jan 1, 2003

By Takahiro Miki

Soldering material widely used is Sn-Pb alloy, which have low melting point and excellent electrical, strength properties and wettability. However, Pb is one of the toxic elements, which is undesirable due to environmental and safety reasons, thus Pb-free alternative alloy is preferred for new soldering materiaL Sn-Ag and Sn-Zn based alloys have been viewed as very promising candidates, among many potential substitutes. Addition of third element to these alloys will decrease melting point of the alloys. Hence, Sn-Ag-In and Sn-Zn-Mg alloys are expected to be suitable for replacing Sn-Pb solder alloy. In order to dcsign new Pb-free soldering materials, it is crucial to understand precise thermodynamic properties and phase diagrams of alloy systems. In the present work, ion current ratios of Ag to In and Mg to Zn were measured for Sn-Ag-In and Sn-Zn-Mg alloys by mass spectrometry, respectively. Also, the authors reviewed the thermodynamic properties of terminal binary alloys determined by other researchers and evaluated a thermodynamic functions to express the excess Gibbs free energy of each binary alloy. Thermodynamic functions to express the excess Gibbs free energy of liquid Sn-Ag-In and Sn-Zn-Mg ternary alloys were determined, utilizing the assessed Gibbs free energy of terminal binary alloys with the measured ion current ratios using mass speetrometer.

Jan 1, 2003

By Mingming Zhang, Ramana G. Reddy

"Carbon dioxide (CO2) is one of the most common by-products produced during light metals production. It is considered to be the cause of greenhouse effects. Efficient reduction of CO2 can help minimize the rate of global warming and improving energy sufficiency. In this paper, a novel light metal production process was developed using ionic liquid electrolytes. This process has significant advantages compared to the traditional high temperature processes such as zero CO2 and CF4 emission, low energy consumption due to the low temperature operation and nonconsumable electrodes. Two types of anode materials (graphite, extruded carbon) were tested in electrolysis experiment. The results showed that both anode materials were stable (negligible weight loss). However, the extruded carbon was found to be superior to graphite in terms of current density and current efficiency. The calculated energy consumption for aluminum production was less than 10 kWh/kg at current densities up to 300 A/m2.IntroductionGlobal demand for ultra-light, ultra-strong, recyclable metals is growing as the world switches to low-emission vehicles, energy-saving devices and sustainable products. Aluminum demand is forecast to climb by 30 percent; magnesium demand by 200 percent, while for the emerging industrial light metal, titanium, the demand is expected to be at least double in the next decade. However smelting of light metals is the most energy intensive among all the steps of light metals production. For example, on an average it takes about 15.7 kWh of electricity to produce one kilogram of aluminum from alumina [1, 2, 3]. Advancements in energy efficiency have been steady, but slow, and most U.S. aluminum smelting production operates at 95% current efficiency. Besides high energy consumption, another major concern of the light metals smelting process is the emissions of greenhouse gases (GHG). Electrolysis green house gas emissions in the Hall-Héroult process can be split into three groups: 1) reduction reaction emissions, carbon dioxide (CO2) and carbon monoxide (CO); 2) process upset perfluorocarbons emissions; and 3) hydrogen fluoride (HF) formed from the moisture (H2O) present in the raw materials [2, 3]. Hydrogen fluoride gas can be captured and returned to the cells by the alumina dry scrubbing system used in modern facilities. A total of 5.31 kilograms of CO2 is generated from the reduction process for each kilogram of aluminum produced in the average U.S. primary facility. The perfluorocarbon emissions are related to the “anode effect.” If the concentration of alumina in the bath becomes too low, other reactions between the carbon anode and the bath occur and tetrafluoromethane (CF4) and hexafluoroethane (C2F6) are generated. These gases have high global warming potentials (GWP), which is a ratio developed to compare the ability of each greenhouse gas to trap heat in the atmosphere relative to carbon dioxide"

Jan 1, 2008

By G. Glinski, K. A. Pericleous

"Recent advances in new computational modelling techniques such as Lattice-Boltzmann and Dissipative Particle methods offer the prospect of simulating complex fluids such as colloidal and dense suspensions in industrial processes. They are referred to as mesoscopic methods since they lie between molecular dynamics at a microscopic atomistic scale «lO-9m) and traditional macroscopic CFD methods (> 1O-2m). The models behave like a 'coarse-grained' gas consisting of fictitious interacting particles, which are much larger than the real molecules of the actual fluid they represent. Inter-particle forces are set so that the collisions collectively mimic the phenomenological transport properties and flow of the underlying fluid at a macroscopic scale.Much of the developmental work to date has focused on laying theoretical foundations based on thermodynamic and kinetic theory. Successful applications include predictions of macroscopic transport properties of complex fluids and flows in porous media and filters. With the constant increase in computational power, these mesoscopic methods are now sufficiently developed to determine their suitability to simulate complex fluid flows in real industrial processes. This work describes the application of meso scopic methods to the stencil printing of solder pastes in the assembly of electronic components. The aim of this work is to assess the ability of these methods to study the transport mechanisms of individual solder particles suspended in the flux solvent as they enter and fill the micro-apertures of a stencil. This paper demonstrates the coupling of such mesoscopic methods to continuum CFD methods to predict the flow of dense suspensions (i.e. solder paste) in industrial processes."

Jan 1, 2001

By R. J. Chesher, J. C. Anzalone, T. F. Krusmark

The BHP Copper Refinery at San Manuel, AZ employs conventional electro-refining technology, plating at a current density of 335 A/m2 on six kilogram copper starter sheets. In 1995, a combination of variable anode chemistries and increasing current density in the tankhouse created periods of increased bismuth in cathode. Bismuth in electrolyte was minimized by bleeding electrolyte to the nearby BHP leaching facility. However, the expected drop in cathode bismuth was not achieved. Investigations indicated that starter sheets contained a significant concentration of bismuth. The bismuth was found to occur in combination with antimony on the surface of the sheet adjacent to the mother blank. Studies were conducted to determine the mechanism by which Group VB elements are incorporated into the starte sheets. Operational practices were introduced to minimize bismuth in starter sheets and improve cathode quality.

Jan 1, 1997

By Lianjun Liu, Ying Li, Qianyi Zhang

"Photocatalytic reduction of CO2 by H2O for production of Cl fuels (CO and CH4) was studied using copper and iodine co-modified TiO2 (Cu-IffiO2) nanocomposites, with copper deposited on the surface and iodine doped in the lattice. The nanocomposites were prepared via a combined hydrothermal and wet impregnation process. All I-doped samples demonstrated visible light activity. Under UV-vis irradiation, co-modification of Cu and I significantly increased TiO2 photoactivity compared with bare TiO2 or those modified with only one species.IntroductionThe photoreduction of CO2 into fuels on photocatalysts such as TiO2 has been regarded as an important approach to solve both energy shortage and globe warming problems [1]. However, the wide band gap and fast recombination ofphotoinduced hole (h+) and electrons (e"") limited the application of TiO2 in CO2 photoreduction reaction. Extensive research has been conducted to improve the photocatalytic ability ofTiO2 by depositing or doping foreign ions that can enhance charge transfer and/or creates intra-band-gap states to induce visible light absorption at the subband- gap energy. Compared with mono-doping, co-doping of metal/nonmetal species has been reported to have higher photocatalytic activity for TiO2 [1-3]. Our previous studies showed that Cu deposited on TiO2 [4] or iodine doped in TiO2 [5] significantly enhanced the catalytic efficiency for CO2 photoreduction and increased the response to visible light. We hypothesize that there could be a synergetic effect if TiO2 is co-modified by both Cu and I species resulting in further improvement in CO2 reduction efficiency. In this work, we synthesized and characterized Cu-IffiO2 samples and investigated their activity toward CO2 reduction under visible and UV-vis illumination, respectively.Experimental MethodsMaterialsTitanium tetra-isopropoxide (TTIP, 98%) and isopropanol (C3HsO, 99.8%) were purchased from Acros Organic. Iodic acid (HIO3,99.8%) and Copper Chloride (CuCh, 99.9%) were purchased from Alfa Aesar. All other chemicals were analytical grade and used without further treatment."

Jan 1, 2012

By Mohamed Ahmed, A. Kawy

"Smelting of scrap copper and residual anodes and cathodes carried out in a reverberatory type furnace. In this, deoxidation process is carried out by wood, which acts as a resource of reduction gases such carbon monoxide, hydrogen and methane. Use of wood causes the formation of soot pollutants and efficiency of oxygen removal from copper is low leading to added costs in removing contaminants. This expensive problem was solved by using of reformed natural gas as a source of reduction gases (CO+ H2).IntroductionThree reverberatory furnaces were used for smelting of scrap copper and residual anodes and cathodes. Each furnace had a 7tpd capacity and was operated at 1183 °C.In this furnace, Step1-compressed air supplied by tubes from the side of the furnace to remove sulfur from copper matte by oxidation .The copper is also oxidized to copper oxide .[1]Step 2- copper from matte is deoxidized by a reductant. Typically deoxidation process is carried out using wood as a resource of carbon monoxide, hydrogen and methane which are the reduction gases. Use of wood causes the following:1- Forms soot pollutants2- Oxygen removal efficiency from copper is low; more contamination in copper matte increased energy in deoxidation3-the process is highly expensive.In the recent trends, this problem has been solved by using reformed natural gas as a source of reduction gases (CO+ H) .This results in 1-Reduced pollution during smelting.2- High efficiency in the removal of oxygen from copper to produce oxygen free copper. The surface of copper produced from this method is smooth which helps in forming and machining.3- Low cost and natural gas is more readily available in Egypt than wood."

Jan 1, 2010