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By Yuanyuan Zhang, Patrick J. Masset

"The reduction of FexO in slag is one of the fundamental reactions in iron and steelmaking technology, including the blast furnace process (BF). Experiments on the reduction reaction of iron oxide using CaO-SiO2-Al2O3-FexO-C mixtures were carried out using thermogravimetric analysis (TGA) under reducing conditions at temperatures up to 1100°C. The composition of the primary slag was chosen so that the FexO concentration varied between 0 and 75 wt % and the CaO/SiO2 ratio being kept constant to 0.90. From the TGA curves recorded isothermally at different temperatures the kinetic parameters of the iron oxide reduction were determined.IntroductionIn blast furnace the iron ores and coke are charged in layers from the top. The reduction of iron oxide by coke is one of the fundamental reactions in the blast furnace process. Although a great amount of work has been done on the topic of reduction of composites [1, 2, 3], gasification of carbon [4, 5] and reduction of iron oxides by CO [4, 5, 6], the mechanism of reduction in iron oxide - carbon powder mixtures is not fully understood. Fruehan [1] and Rao [2] studied the reaction rate of the reduction of iron oxide by different types of carbon and concluded that the reaction mechanism is controlled by the oxidation of carbon at temperatures up to 1200°C. Rao [2] studied the reaction of hematite with graphite as carbon source up to 1080°C. An activation energy close to 300 kJ/mol was calculated within the temperature range of 950°C to 1087°C. In his study, Fruehan [1] determined the rate of reduction of Fe2O3 and FeO by coal, coke and coconut charcoal as carbon sources within the 900°C to 1200°C temperature range. He found that the reduction of Fe2O3 by carbon occurs in two stages and that the reduction of Fe2O3 to FeO is faster than that of FeO to Fe. This is due to the fact that the CO2/CO equilibrium ratio is higher, and hence, the rate of oxidation of carbon is faster. Fortini and Fruehan [3] have studied the reduction reaction of wustite by graphite and wood charcoal. They found that the wustite reduction can have a significant effect on the overall rate of reduction in composites at high temperatures or in the presence of a large excess of carbon. The calculated activation energy of the reduction reaction by wood charcoal was close to 368 kJ/mol, while the activation energy of the reduction reaction by graphite was 444 kJ/mol."

Jan 1, 2011

By Harald Laux, Stein Tore Johansen

The plunging jet in tapping of steel from converters or electric arc furnaces entrains gas into the steel bath contained in a ladle. Gas entrainment rate and the effect of the gas on the flow pattern in the ladle are studied by means of Computational Fluid Dynamics CFD. The work focuses on the mathematical modeling. Two numerical methods, one for free-surface flows and one for dispersed multiphase flow are combined. A transport equation for the average bubble diameter that incorporates the effect of coalescence and breakup is presented. Results from computations for one ladle and tapping configuration are shown. Our findings indicate that the gas entrainment rate is affected by the material properties of the liquid in the sense that the material properties determine the shape of the jet. Moreover, bubble sizes in the range of two-orders of magnitude are predicted in the ladle. The dispersed diameter model seems to work well. It showed the expected response to material parameters and the turbulent field. However, the presented analysis is just a first step that was limited due to certain simplifications. In order to obtain better insight in the tapping process improvements of the analysis seem necessary.

Jan 1, 1999

By R. P. King

The essential features of an image analysis system for the measurement of mineral liberation are described. Good procedures for image acquisition and image processing prior to image analysis are defined. The basic stereological methods for the measurement of volume fraction, surface area per unit volume, particle size distribution and liberation spectra are given. The appropriate methods for fractal correction when measuring perimeters of irregular features and for frame correction when measuring linear intercepts are developed. Practically useful and accurate procedures for the stereological correction of particle size and liberation distribution methods are given.

Jan 1, 1995

By Gerardo Fuentes

The stoichiometry and kinetics of the hydrothermal reaction of enargite in copper sulphate solutions was investigated in the range 140–300 °C, and particle size under 15 and 50 μm. The stoichiometric experiment was performed at 300 °C, using one gram of sample (96% enargite, 4% tennantite) and 100 mL of copper sulphate solution (10 gpl) at 1.2 pH. Enargite reacted completely after 80 min. A solid product was obtained and characterized by XRD. The main product was chalcocite (M) and some traces of djurleite and chalcocite (Q). Tennantite did not react under these conditions. The kinetic experiments were conducted at 140 °C, 190 °C, 250 °C and 300 °C. From fitted data and Arrhenius equation the calculated activation energy (Ea) was 51 kJ/mol. According to the hydrothermal transformations studied, the reactivity of different phases found in the copper concentrates was bornite > chalcopyrite > covellite > sphalerite > pyrite > enargite > tennantite.

By H. Kaffash

Ferromanganese is a ferroalloy with high manganese content which finds many uses for example as deoxidizer in steelmaking industry. However, there is very little data on the dissolution rate of carbonaceous materials in Mn containing metals. In this paper, the kinetic analysis of carburization reactions is investigated for Mn–Fe alloys. Dissolution rate of graphite in pure iron and four different alloys with 10 wt%, 40 wt%, 60 wt% and 85 wt% manganese at 1823 K was studied. Results showed that the dissolution rate of carbon from graphite increased with increasing time for all alloys. The dissolution rate constant increased with the increasing manganese content from 6.5 × 10−3 cm/s for 0%Mn to 23.6 × 10−3 cm/s for 85%Mn.

By Yun Li

An innovative lead recycling process from scrap lead-acid battery paste is presented. The novelty in the process is avoiding SO2 generation and emission by using reductive sulfur-fixing technique. Iron-bearing secondary wastes produced from metallurgical industry were utilized as sulfur-fixing agent to capture sulfur in the form of FeS (s) instead of generation of SO2 (g). Na2CO3 molten salt was added to the smelting system to speed the reactions and improve valuable metals’ recovery and sulfur-fixation efficiency. Furthermore, this process can simultaneously co-treat various lead and iron-bearing wastes. At the same time, some precious metals, such as Au and Ag, contained in iron-bearing wastes can be recovered. The feasibility and reliability of this process was investigated thermodynamically and experimentally with the help of HSC 9.0 database and XRD and SEM-EDS analysis. A possible reaction mechanism and path in PbSO4–Fe2O3–Na2CO3–C smelting system was also clarified.

By G. A. Irona

Solids injection into non-ferrous converters and furnaces is becoming increasingly important for concentrate injection, removal of impurities, and recycling of dusts and other waste materials. The fundamental design aspects of these technologies will be reviewed, including gas and particle trajectories, lance clogging, heat transfer, and mass transfer including reaction rates and mixing. The use of soda ash for removal of impurities such as antimony and selenium will be used as an example of versatility of powder injection processes.

Jan 1, 1993

By Bora Derin, Sertac Yazici, M. Seref Sonmez

"In this study, the recycling conditions of waste liquor obtained after the production of tungsten boride powder from calcium tungstate by self-propagating high temperature synthesis (SHS) and the following hydrochloric acid leaching were investigated in detail. Environmentally unfriendly and extremely acidic (pH~ -0.3) liquor consisting of calcium, magnesium, and boron ions was treated with 1 M sodium carbonate solution to precipitate magnesium carbonate and calcium carbonate phases. The obtained amorphous precipitates were heated up to the temperature of 400°C for re-crystallization. As a result, MgO, CaC03 and CaMg(C03)z phases were obtained, while sodium, boron, chlorine ions were remain in the solution. The present study is still in progress.IntroductionSelf-propagating high temperature synthesis (SHS) is one of the techniques used in the production of a variety of advanced ceramics, inter-metallic, organic and inorganic compounds, oxygen free single crystals, and polymers [ 1, 2]. The reaction becomes selfsustaining and propagates in the reactant mixture, after initiation in SHS process. SHS products may contain the mixture of several unwanted compounds and elements. Therefore following acidic leaching process may be needed to purify the target product. In the previous study, calcium tungstate (Ca W04), magnesium (Mg) and boric acid (B20 3) mixture were reacted to produce tungsten boride powder by SHS process according to the Reaction 1. Then, magnesium and calcium containing byproducts (i.e. MgO, Mg3B206 and Ca3B206) found in the SHS product were leached out by using concentrated hydrochloric acid (HCl) solution to obtain pure tungsten boride powder [3].Ca W04 + 0.5B203 + 4.5Mg = WB + 4.5Mg0 + Cao (1)After the leaching, filtrate solution consisting of different amounts of magnesium, calcium, and boron requires additional treatment for the environmentally acceptable disposal.Several works were carried out about magnesium precipitation conditions and kinetics from brines. Rabadzhieva et al. investigated the precipitation of Mg(OH)z from brines by using NaOH as well as caustic soda [ 4]. Turek ve Gnot investigated the precipitation efficiency of Mg(OH)z for the temperature range between 10-40°C, while the reaction was kinetically experimented by Alamdiri et al [5, 6]. Homogeneous precipitation of nesquehonite (MgC03.3H20) by the reaction of MgCli with (NH4)2C03 in supersaturated solutions and factors that influence the precipitation of MgC03.3H20, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied by Wang et al [7]. The precipitation of Mg(OH)z by calcium hydroxide from aqueous solutions was studied by Baird et al. [8]. Stratful et al. focused on conditions influencing the precipitation of magnesium ammonium phosphate from wastewaters [9]. 1031"

Jan 1, 2011

By Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996

By Graham Cooke, Abhishek Lahiri, Animesh Jha, E. Jeya Kumari

"CO2 reduction by alternative energy devices such as wind-power, electric vehicles utilize rare-earth elements (REE) in several forms; such as in piezo-electric devices, batteries and magnetic materials. In 2010, the 95% of Rare Earth supply is controlled by China, compared to USA being dominant supplier in the 1980s. The dependence upon a single source of lanthanides has prompted the utilization of lower grades of titaniferous mineral concentrates, which often have rich seams of REE. We propose a new methodology, which utilizes the low-grade minerals for the extraction of synthetic rutile and also significant quantities of REE. We demonstrate the alkali roasting of lower grades of mineral concentrates and subsequent leaching in an aqueous medium for preferential flocculation of REE during the extraction of synthetic rutile. Changes in mineral structure during alkali roasting and leaching determine flocculation of REE and permit their separation at the front end of unit process.The physical chemistry and crystal structure of minerals in equilibrium with alkali and aqueous medium play an important role, which we explain by demonstrating the changes in the crystal structure. The quantification of separation of RE oxide via chemical analysis suggests that it may be possible to separate rare-earth oxides between 50 and 80% of the initial concentration in the non-magnetic fractions of ilmenite, for example. The microstructural and X-ray diffraction analysis points out that the presence of alumina and roasting with potassium based alkali enhances the separation and flocculation of rare-earth elements at the front end of the process after roasting. The process allows the recovery of CO2 generated by recycling into the process for the regeneration of alkali."

Jan 1, 2011

By Rolando Campos

Until 1970, the Caletones Smelter of CODELCO-CHILE, División El Teniente, operated under the conventional pyrometallurgical process used by most of copper smelters. The annual copper production varied around 165.000 tons. The failure in the commissioning of the "oxygen smelting" technology in Peirce- Smith converters (1970-1972), forced further introduction of transcendental changes in the Caletones smelter operating scheme. Implemented technological innovations were based on wide studies and research works performed by División El Teniente. This paper presents a summary of technological modifications introduced, their impact on production and energetic performances, and short and medium terms improvement plans.

Jan 1, 1993

By Zhihong Liu

In recent years, the removal of arsenic from different types of high arsenic containing materials produced in nonferrous metallurgical processes have been experimentally studied in the complex materials processing research group from Central South University. These materials include arsenic and antimony bearing flue dust, arsenic sulfide residue and arsenate bearing flue dust. The separation of arsenic from other valuable metals was carried out hydrometallurgically; for each type of arsenic bearing material, different processes have been employed individually to remove the arsenic effectively. In this paper, the flowsheets and typical experimental results have been summarized.

By Thais Cristina da Costa Caldas, Alline Sardinha Cordeiro Morais, Carlos Maurício Fontes Vieira, Sergio Neves Monteiro

"This work has as its objective to evaluate the firing behavior of a kaolinitic clayey body from Campos dos Goytacazes-RJ incorporated with flat glass waste (FGW) from civil construction. Incorporations of the waste, with a particle size less than 74 µm (200 mesh), were performed in the red ceramic in the following amounts: 0, 2.5, 5 and 10 wt%. Specimens were prepared by uniaxial press-molding and then fired at 850 and 1050°C. The characterization of FGW was done by X-ray Fluorescence. The physical and mechanical properties evaluated were: linear shrinkage, water absorption and flexural rupture strength. The microstructure of the fired ceramics was evaluated by optical microscopy (OM). The obtained results showed that the flat glass waste can be used as a component of ceramic bodies once it was noticed tolerable modifications of technological behavior.IntroductionBrazil is one of the world’s largest producers and consumers of clayey ceramic. Campos dos Goytacazes is located in the north of the State of Rio de Janeiro, southeast of Brazil, it’s known as a large producer of red ceramics. It is estimated that the production of bricks can reach 1 billion pieces per year [1].Nowadays, recycling processes became more and more important, due the generation of wastes in large scale and the preoccupation with environmental. The amount of glass waste has been exponentially growing with the growth of the population. It is estimated that the amount of discarded glass as bottles, construction windows, packing and other glass waste represented in 2006 an amount of 7.5% of the total weight of the world´s domestic garbage [2]."

Jan 1, 2012

By F. A. Myzenkov

The technology developed by the authors uses new methods for raw material smelting in electric furnaces, a new autogenous method and apparatus for subliming smelting for antimony trioxide production and separation of antimony and gold. Concentrate produced from the ore deposits in Yakutia has the following average contents of main constituents, % by weight: 29.4 Sb, 1.2 Fe, 13.1 S, 40.0 SiO2, 0.2 As, 2.6 CaO and 45 g/t of Au. Unlike the technology used abroad a new autogenous method makes it possible to increase considerably specific capacity and reduce gold losses with antimony trioxide by several times. At the same time mineralogical composition of trioxide has improved considerably ? it has mainly a cubic base with prevalence of senarmontite. The content of a main component (Sb2O3) in the final product has increased from 99.0% up to 99.6% which means better quality and makes it suitable for use in special technologies. Despite a lower antimony content of the concentrate (29.4% as compared with over 33% as common in the world practice), an antimony recovery of 85.3% into a commercial-grade product has been achieved, as well as a gold recovery of 96.65% into a gold-antimony alloy. The technology for processing gold-antimony materials developed and introduced at the Ryaztsvetmet plant is unique in the world with respect to gold recoveries.

Jan 1, 2006

By Jay Black

In the thiosulfate gold leaching process gold is oxidized to Au+ by a copper(II) ammine catalyst and complexed by thiosulfate. Copper(I) complexes, formed during gold oxidation, are reoxidised to Cu(II) complexes by oxygen. In this study, we present the results of a spectrophotometric study of the Cu(I)-NH3-Cl system, which follows on from our recent investigations of speciation in the Cu(I)-Cl and Cu(I)-S2O3-Cl systems and is part of a detailed study of copper(I) speciation associated with the gold leaching process. Formation constants for Cu(I)-NH3-Cl complexes have been determined by modeling the systematic changes in the UV spectra that occur as the concentration of the components is varied. The analysis of the data indicates that three Cu(I)-ammonia complexes are present, i.e., [Cu(NH3)2]+, [Cu(NH3)Cl2]- and [Cu(NH3)2Cl] and their respective log Kf values are 11.13, 8.33 and 10.79 at 25°C. Investigations of the oxidation of Cu(I)-NH3-Cl solutions by oxygen in the atmosphere are also presented. These experiments indicate that the reaction of copper(I) complexes progresses through various intermediates. The presence of many copper(I) and copper(II) complexes in ammonia thiosulfate solutions complicates the task of determining optimal conditions for gold leaching. Further studies are needed to identify the complexes and chemical processes that are important in the Cu(I)-NH3-S2O3-Cl system.

Jan 1, 2003

By S. G. Kumar

The performance of nickel based high temperature materials is directly related to their microstructure, which is controlled by the various processing steps. Nickel base alloys are melted and refined by a variety of processes that include Vacuum Induction Melting (VIM), Vacuum Arc Remelting (VAR) and Electroslag Remelting (ESR). The limitation of VIM is that the metallrefractory reactions lead to the disintegration of the crucible and hence contamination of the product due to macrosegregation. This macrosegregation is alleviated to some extent by controlling the solidification in VAR. The main attraction of ESR is its ability to produce a clean product by controlling the deleterious inclusions. In recent years Electron Beam Melting (EBM) is emerging as an alternative to the VIM, VAR and ESR. This paper reviews the current status of these processes and outlines the scope for further improvements in the processing technology.

Jan 1, 1993

By Jinxing Ji

Several fundamental aspects related to the nickel electrowinning from chloride electrolytes have been addressed in this paper. The thermodynamic study includes the activity coefficient of the hydrogen ion and the speciation diagram of NiCI2 solutions. The activity coefficient of the hydrogen ion (YH+) was calculated and estimated experimentally using a combination glass pH electrode. It was found that YH+ was greater than one in concentrated NiCl2 solutions and increased significantly with increasing NiCl2 concentration. The speciation diagram for NiCl2 solutions was plotted with YH+ and the effect of the ionic strength on the equilibrium constants being taken into account. It was discovered that the predominant nickel species in the acidic region were Ni2+ and NiCI+ in 0.937 M NiCl2 solution at 25°C. Electrodeposition tests demonstrated that higher Nit' concentration in the electrolyte improved the current efficiency of nickel electrodeposition (CENi). The additions of H3BO3, and NH4Cl increased very little the current efficiency of nickel electrodeposition at pH 1.5 and temperature 60°C. However, the addition of sulfate decreased the current efficiency of nickel electrodeposition. Nickel electrodeposition was also found to be a steady-state process since the amount of acid added to the electrolyte at a constant pH increased linearly with time during galvanostatic electrodeposition. The cathode surface pH during nickel electrodeposition was measured using a flat-bottom combination glass pH electrode and a 500-mesh gold gauze as cathode. The cathode surface pH was found always to be higher than the pH in the bulk electrolyte, and if the current density was sufficiently large, it would eventually reach a level causing precipitation of insoluble Ni(OH)2(s) on the cathode surface. Rotating disc electrode studies revealed that the rate of nickel electrodeposition was first order with respect to the activity of nickel ion and zero order with respect to the activities of chloride and hydrogen ions. The rate of hydrogen evolution was found to be first order with respect to the activity of hydrogen ion and to be zero order with respect to the activities of nickel and chloride ions. These findings indicate that nickel deposition and hydrogen evolution proceed independently.

Jan 1, 1995

By J. Murdoch Mackenzie

Two commercial nickel solvent extraction plants treating laterite leach solutions and using LIX®84-I have been operated in Australia. These circuits employ similar extraction chemistry but differ in their leaching and stripping operations. An alternative process involving elements of both can be conceived. The preparation of the feed solution to solvent extraction plays an important role in nickel extraction using LIX®84-I and the special features of manganese removal and cobalt oxidation in the preparation of the PLS are discussed. This paper compares these three circuit configurations with special reference to the extraction and reductive stripping of cobalt, the transfer of zinc and copper to the strip aqueous, ammonia transfer and sulfur transfer. The potential degradation of the organic and remediation using re-oximation is discussed. Keywords: Nickel, Solvent Extraction, Oxime

Jan 1, 2004

By Tom W. Gonzales

Magma Metals Company commissioned a 3000 tpd Outokumpu flash smelting furnace in July 1988. Through September 1992 the PSP has smelted a first campaign record 4.1 million tons of concentrate. This paper discusses modifications made to the original process equipment to overcome design flaws as well as future design changes currently under consideration.

Jan 1, 1993

By A. V. Tarasov

In order to improve the efficiency of hydrometallurgical processing of pyrrhotite concentrates, an integrated set of research has been carried out to investigate the use of sulfur dioxide in individual unit operations and as a leaching agent in the autoclave process as a substitute for oxygen. Treating iron-containing raw materials for production of nonferrous metals are based on the selective reaction of SO2 with iron sulfides and oxides. Iron is dissolved as sulfate, which can be treated in a separate circuit to produce iron-containing pigments or it can be disposed of after neutralization. Nonferrous and precious metals contained in pyrrhotite concentrate do not react with sulfur dioxide and remain virtually completely in the solid phase, i.e. high-grade sulfide concentrate to be treated by hydro- or pyrometallurgical methods. Elemental sulfur formed in the process of leaching is separated from the pulp in granulated form as a result of the use of special surfactants. The process of sulfide concentrate leaching with the use of sulfur dioxide is conducted at temperatures above the sulfur melting point (119°C) with distributed feeding of surfactant and under a partial pressure of sulfur dioxide of up to 0.3 to 0.5 MPa.

Jan 1, 2006