Search Documents

By Clemens Schmetterer, Patrick J. Masset

"The surface tension represents an important property for the modelling of high temperature processes. In this study the surface tension of two Al2O3 – CaO – SiO2 model slags and the influence of the admixture of 5 up to 30 wt.% FeO were studied. The surface tension measurements were carried out using the sessile drop technique on BN substrates under Ar atmosphere (10-6 atm O2) up to 1500 °C.IntroductionThe aim of VIRTUHCON1 is the virtualization of high temperature conversion processes, a task that requires thorough understanding of these processes. In many of these conversion processes slag plays an important role to control the properties of the product, to protect the reactor lining or simply as waste. Slag surface tension is one of the materials properties that is needed for the description of such processes, since it influences the interactions between the components in the reactor, e.g. at the slag – Fe interface in the blast furnace.Surface and interfacial tensions have thus received considerable attention in research, but the number of investigations in this particular pseudo-quaternary system is surprisingly low. Furthermore, the literature data are subject to different measurement conditions and techniques which complicates the data analysis and comparison.The slag atlas [1] offers a compilation of the available literature until 1986 (shown in Table I), but literature search has not revealed more recent studies of this system until now. For example, Elliott and Mounier [2] determined the surface tension of ACSF slags using the double tube maximum bubble pressure technique at 1200 °C. They kept their slags in contact with Cu-S-F mattes, and the slag therefore contained a certain amount of sulphur which acts as a surfactant and lowers the surface tension. The compositions of their slags were scattered over a wide composition range and they did not use a common ACS base mixture for their tests, either. The surface tension values vary between 417 and 446 mN/m, but due to the reasons just mentioned no trend in the measurements can be observed and the influence of FeO admixture on the surface tension cannot be deduced. Further information including the temperature dependence is available from Pavlov et al. [3], Ishchanov and Shushkov [4] and Murav’eva and Kaplun [5]; the diagram on page 446 in Ref. [1] has been drawn from these sources. Both positive and negative temperature coefficients are reported in these works. SiO2 is the only pure constituent that has a positive temperature coefficient [6], but a correlation of the temperature coefficient with the SiO2 content was not found to be conclusive."

Jan 1, 2011

By J. T. I. Poijärvi

The smelter off-gas cleaning and the weak acid treatment at Outokumpu Harjavalta Metals Oy are presented and described in this paper. The smelter consists of the copper and nickel smelters and the acid plant of three separate acid plants two of which are double contact and one single plant and of one liquid sulphur dioxide plant. The preliminary cooling and flue dust separation of the smelter off-gases from the copper and nickel flash smelting furnaces and converters in the waste heat boilers and in the hot electrostatic precipitators are described. The final cooling and cleaning of the gases in the scrubbers at the sulphuric acid plant and the treatment of the weak acid in the vacuum and in the submerged combustion evaporators for the removal of impurities are pre¬sented as well as the treatment of the condensates from the evaporators. The attention is paid to the generation of sulphur trioxide in the smelter off-gas and to the treatment of that in the weak acid bleed-off and to the utilization of the treated acid.

Jan 1, 1992

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By Fathi Habashi

While it is commonly known that the precious metals and to some extent copper occur in the native state, it is less known that mercury, iron, nickel, and cobalt do occur also in the native state; the last three (Fe, Ni, and Co) usually occur together in form of an alloy. The particle size varies greatly from less than 10 microns (gold and mercury) to about 400 tons boulders (copper).

Jan 1, 1993

By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012

By R. Burkhard

Recovery of metals from complex mixed wastes is a challenging task of modem material and waste management strategies. Thermal methods are an important tool in this respect. Plasma turned out to be particularly useful for treatment of complex or toxic wastes and residuals. In order to study plasma processes at reasonable costs, a pilot plasma plant has been used and wastes like ~pent Raney-Nickel catalysts, copper and ah.:lminum drosses, and. other metal containing wastes were investigated. The paper summarizes the most significant findings

Jan 1, 1995

By S. M. Hay

The zinc content of blast furnace and basic oxygen furnace dusts is low compared with electric arc furnace dusts and it is generally not economical to treat the dusts to recover zinc. However, they have a high iron content and removal of the zinc would allow recovery of the iron values. A literature review and thermodynamic analysis was undertaken and, as a result, several smelting options were identified. This paper describes experiments undertaken to develop understanding of metallurgical aspects of these processes which are not amenable to theoretical analysis. Dusts from an Australian steelworks were characterised in order to determine their mineralogical make-up and the form of the iron. The processing aspects investigated in the laboratory were slag-metal equilibrium and solid-state pre-reduction using reducing gases of compositions expected from bath-smelting processes. Particular attention. was paid to the deportment of zinc, sodium, potassium, phosphorous and sulfur between the phases formed during smelting and pre-reduction. The smelting results indicate that less than 10% of the zinc, sulphur, sodium and potassium report to the metal. About 99% of the zinc and potassium and about 80% of the sodium could be volatilised from the dusts by reducing them at 1,000°C with mixtures of CO, CO2, H2 and H2O even when metallic iron was not formed. The experiments indicate that smelting of blast furnace and basic oxygen furnace dusts should produce hot-metal of a composition which can be blended into the main stream of hot-metal in the steelworks.

Jan 1, 1994

By Cameron Hams

Noranda's Process Reactor and Codelco's Teniente Converter are physically similar vessels, which leads to the commonly held misconception that the two processes are the .same. However, notable differences in chemistry, operating philosophy, and construction make them quite dissimilar. This paper compares and contrasts the Noranda Reactor and the Teniente Converter, and attempts to explain some of the apparent differences in behaviour and performance. The results of a worldwide survey of most operating Noranda Reactors and Teniente Converters, along with those processes that have ceased operation or are planning to be started-up in the future, are presented.

Jan 1, 1999

By Chengxian Lui

Detailed mineralogical and metallurgical investigations were carried out on a phosphorous-bearing manganese carbonate ore from the Huayuan manganese mine, Hunan, China. Microprobe analyses indicate that the Manganese occurs mainly in calc-rhodochrosite and in rhodochrosite. The cOll'pOsitional range of these manganese carbonate minerals is 50 -80 % MnOJ3, 0 -35 % CaOJ3, 5-35 % MgC03 and 0 -15 F~. The manganese carbonate minerals are very fine grained, IOOSt are between 4.6 and 9.4 1m in diameter. The small grains are clustered into aggregates that form bands 0.5 to 10 rnn wide. The phosphorous-bearing mineral in the ore is fluorapatite and is in grains that are generally smaller than 6 1m in diameter. Metallurgical tests show that it is possible to concentrate the aggregates of manganese carbonate minerals by high intensity magnetic separation, and to reduce the phosphorous content by rpasting the concentrate to convert the manganese carl::x>nates to insoluble hausmannite, and then leaching the roast product with HCI to dissolve the fluorapatite.

Jan 1, 1989

By E. Charles Abbey

Manganese in electrolyte has both beneficial and detrimental effects in Zn electrowinning. Mn oxidizes to form MnO2 on Pb–Ag anodes, cell walls and pipes. MnO2 reduces anode corrosion but also leads to short circuiting and maintenance issues. MnO2 is thought to interact with chloride ions and produce oxidized chlorine species. The interactions between Mn and Cl are not well understood. Therefore, two sets of 45+ day bench scale experiments were conducted to investigate the effects of the manganese to chloride ratio on anode corrosion rate and electrolyte chemistry using rolled Pb–Ag anodes. Daily manganese and chloride losses from the electrolyte appeared to be correlated. Increasing the average Mn/Cl− ratio from ∼7:1 to ∼11:1 reduced the anode corrosion rate. Increasing the ratio above 11 did not reduce the corrosion rate further. Anode scales produced with Mn/Cl− ratios at and above 11:1 contained some γ–MnO2 while scales formed with ratios less than 11:1 did not.

By S. A. Shuey

The present industrial practice used to separate aqueous cobalt from nickel is multistage solvent extraction processing. This paper describes a different but simpler treatment technology. The proposed technology has been applied to cobalt/nickel hydroxide intermediate solids produced from the treatment of Electrochemical Machining (ECM) waste sludge, The process consists of dissolving the cobalt/nickel hydroxides in basic cyanide solutions. Cobalt and nickel form aqueous .solution metal cyanide complexes. Nickel can be selectively precipitated from the solution as a nickellic hydroxide solid. Cobalt can be recovered from the leach solution by precipitation of a cobaltous/cobaltic cyanide double salt. The double salt product can then be subsequently treated to produce an appropriate cobalt product. The process chemistry, proposed fiowsheet and preliminary reagent costs are presented and discussed.

Jan 1, 1998

By Joseph Gambogi

In 1998, approximately 57,000 tons of titanium metal was consumed in the form of mill products (1). Only about 5% of the 4 million tons of titanium minerals consumed each year is used to produce titanium metal, with the remainder primarily used to produce titanium dioxide pigment. Titanium metal production is primarily based on the direct chlorination of futile to produce titanium tetrachloride, which is then reduced to metal using the Kroll magnesium reduction process. The use of titanium is tied to its high strength-to-weight ratio and corrosion resistance. Aerospace is the largest application for titanium. In this paper, we discuss all aspects of the titanium industry from ore deposits through extraction to present and future applications. The methods of both primary (mining of ore, extraction, and purification) and secondary (forming and machining) operations will be analyzed. The chemical and physical properties of titanium metal will be briefly examined. Present and future applications for titanium will be discussed. Finally, the economics of titanium metal production also are analyzed as well as the advantages and disadvantages of various alternative extraction methods.

Nov 26, 1999

By Robert P. Stevens

It is important for a refractory supplier to make systematic petro-graphic examinations of products which have been in service in the furnaces and kilns of customers. The petrographic examination of refractory service samples involves the microscopic study of polished and/or thin sections, supplemented by electron probe microanalysis, as well as the bulk chemical and XRD analysis of zones in the samples. The evolution of the A. P. Green Refractories Company petrographic laboratory is described, and the application of petrographic methods is illustrated in the examination of service refractories from a Portland cement rotary kiln and an AOD stainless steel vessel. The objectives of such studies are to assist the customer in the solution of his refractory problems, and to accumulate data which are of use in the design of improved refractory products.

Jan 1, 1981

By Shawn A. Cefalu, Matthew J. M. Krane, Kent J. VanEvery

"Segregation during electroslag remelting (ESR) of a nickel-chromium-molybdenum alloy (Ni-8 wt% Cr-25 wt% Mo) has been modeled. Features of the model include species transport and AC electromagnetic effects coupled with fluid flow, heat transfer, and solidification. The effect of varying ingot diameter and melt rate, on macrosegregation patterns, local solidification time, and liquid pool profiles obtained from this model are demonstrated. The results show that the macrosegregation in the ingots correlates to the filling velocity.IntroductionElectroslag remelting (ESR) is a secondary melting process used to refine the chemical composition and the microstructure of metals. Macrosegregation of solute elements causes defects in ESR ingots, including freckles and the maldistribution of phases. These defects are not correctable through heat treatment due to the large length scales over which they occur. However, the frequency and distribution of these defects may be minimized, or even prevented, through process control based on an understanding of the conditions that lead to their formation.In the past, studies have been conducted on the effect of the process parameters on the shape of the melt pool and the thickness of the mushy zone [1-7]. In these studies, the shape of the liquid pool is determined by consideration of the heat and fluid flow induced by electromagnetic (Lorentz) force and thermal buoyancy. The transport of solute and the resultant solutal buoyancy effects were not considered in these macroscopic models. Defect formation is tied to formation of secondary phases (e.g., freckling and white spots in nickel superalloys) [5,8]. In cases where secondary phase formation is calculated (e.g., [6]), phase fractions are determined using a micro-scale model given the local solidification time (LST) and local thermal history from the macroscale model.Using the local thermal history from the macroscopic transport model to predict microstructure increases the importance of the accuracy of those results. This investigation models the macrosegregation of molybdenum during the ESR of a Ni-Cr-Mo alloy. The effect of macrosegregation on pool shape and depth is demonstrated, along with its effect on the local solidification time. By comparing the relative effects of the melt rate and ingot radius, a better understanding of the factors that affect macrosegregation, and ultimately secondary phase formation may be obtained."

Jan 1, 2004

By Ben Bowman

For certain ferroalloy furnaces, such as ferrochrome or ferromanganese, there is still doubt about the mechanisms operating under the electrode tips. In this paper a model is built that does not call upon an arc. The medium is best described as an electrically conducting slurry, a mixture of liquids, solids and gas. There are two sources of propulsion, the Lorentz force within the conducting part and buoyancy generated by CO bubbles, creating two opposed poloidal circulation loops, downward below the electrode axis and upward further out.

Jan 1, 2014

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

By F. Elgersma

Hydrometallurgical zinc winning processes ?are frequently based on iron containing concentrates which yield a goethite, jarosite or hematite residue. Jarosite or goethite are mostly stored in waste ponds which ,are lined with foil. Water percolating through the pond is withdrawn from the deposit ,and decontaminated before discharge. Despite these measures, more and more pressure is put upon zinc companies to treat their (historical) residues and to produce environmentally acceptable residues. The criterion which determines this acceptability is the potentiality of leaching out hazardous elements by natural processes. This paper provides the comparison of five different process designs for integrated jarosite treatment in a hydrometallurgical zinc winning plant leading to environmentally acceptable residues. The processes are esigned for producing 200 ktons/yr zinc and for treating 80 ktonslyr historical jarosite. Mass and energy balances are used to determme parameters such as: the energy use per ton waste treated and the amount and composition of final residues. The conclusion of the work is that. pyrometallurgical jarosite treatment integrated in hydrometallurgical zinc winning is preferable to hydrometallurgical jarosite treatment. Integrated pyrometallurgical processes lead to a ?smaller quantity of remaining hazardous residues and require less energy.

Jan 1, 1992

By I. Gaballah

Cadmium is toxic to plant, animals and humans. The council directive of the European Communities No 8315 13lEEC has fixed an upper limit of 200 ppb for the release of cadmium in industrial effluents. The conventional method of neutralization/prccipitation ( NIP ) is inefficient to reach this limit. The objective of this study is to test the efficiency of the trees modified bark to remove cadmium cations from industrial effluents after the conventional treatment by NIP. Laboratory scale tests with synthetic solutions show that the cadmium removal depends upon pH and initial concentration. About 99.9 %, 99 % and 96 % of the metal are removed from synthetic solutions containing 10, 100 and 1000 ppm respectively. Pilot plant trials ( 1 m3 ) with an industrial effluent bearing about 500 ppb of cadmium lead to the almost complete elimination of the cadmium ( final concentration is lower than the analytical detection limits < 20 ppb ).

Jan 1, 1994

By Ragnhild E. Aune, Mark William Kennedy, Shahid Akhtar, Jon Arne Bakken

"To determine the heating rate of billets using ‘short coils’, an appropriate correction factor must be applied to the theoretical relationship. In 1945, Vaughan and Williamson published a semi-empirically modified Nagaoka coefficient applicable for moderate frequency induction heating processes (10 kHz). Recently it was demonstrated that the method of Vaughan and Williamson gives <10% error in the estimated power when heating aluminum billets at 50 Hz.In the present study, experiments have been conducted on aluminum billets in order to verify an empirical frequency corrected ‘short coil’ equation. Measurements of electrical conductivity (<± 0.5%), current (± 1%), heat (± 1-3%), and magnetic flux density (± 1-2%) have been performed. The results are compared with 1D analytical calculations, and 2D axial symmetric FEM modeling using COMSOL 4.2®. The frequency corrected equation has proven to provide accurate predictions of power (<4% error) within the frequency range 50 Hz to 500 kHz.IntroductionInduction heating is commonly applied to the re-heating of billets before forging or extrusion processes. The resistive heating produced by eddy currents in the solid or semi-solid work piece during this procedure, is driven by the time varying magnetic flux density in the air-gap between the work piece and the coil. The flux in the air-gap is created by the current flowing in the induction coil, i.e. the magneto-motive force. In Figure 1 it can be seen that the currents present in the work piece are concentrated in the outer ‘shell’, or the first electromagnetic penetration depth (dw), and flow in a direction which opposes the magnetic field produced by the induction coil."

Jan 1, 2012