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By N. L. Piret

In copper smelting minimization of solid waste generation is receiving increased attention with more stringent environmental legislation and lower disposal space availability. Copper smelting slags generally being valorizable, solid waste generation is attributed to the presence in the feed of unvalorizable impurities which do not report to the slag and to the unavoidable formation of contaminated dilute acid solutions which need neutralization. As to unvalorizable impurities, solid waste minimization is achieved by rejecting them in the highest possible concentration. Dilute acid is mainly due to the formation of SO3 in the smelter gases and to the discard of decopperized bleed-off electrolyte. Its generation is substantially lowered by preventing SO3 formation, by converting the dilute acid to a valorizable product, e.g., by thermal decomposition for H2S04 recovery or by precipitation as chemical gypsum, and by suitable treatment of the bleed-off electrolyte for impurity removal. Industrial processes are evaluated and alternatives are discussed.

Jan 1, 1994

By Hiroyuki Matsuura

The effects of P2OS or Na2O addition on the reaction rate of CO2 dissociation on the surface of FexO-base molten oxides was investigated at I 773K by isotope exchange method 1-6. The rate constant decreased with increasing P2Os content of molten oxides and the residual rate constant was observed at high P2OS content. On the other hand, the rate constant increased with increasing Na20 content for FexO-SiO2 melts, The rate constant was evaluated by the composition of oxides and the rate controlling step of CO2 dissociation was discussed.

Jan 1, 2003

By Varadarajan Seshadri

A physical model based on similarity principles was constructed for simulating the RH degasser of CST (Companhia Siderurgica Tubarao, Vitoria, ES, Brazil) to evaluate the circulation rate of the metal which essentially defines the degree of exposure of the metal to vacuum in the chamber and thus of the refining rate. The circulation rate on the other hand will influence the decarburization rate and removal of dissolved gases like nitrogen and hence it is essential to optimise this parameter to get maximum refining efficiency with minimum refming times, thus improving the productivity of the secondary refining process. Mixing characteristics in the ladle is evaluated by pulse tracer addition using conductivity-meters located at the down leg as well as at several locations in the ladle. The influence of gas injection through nozzles in the upleg with simultaneous bottom injection of gas as well as nozzle blockage on the circulation rates were investigated. Also simulation experiments of kinetics of decarburization were carried out using C02 adsorption-desorption process in sodium hydroxide solution as circulating fluid and the effect of, bottom gas flow rate in this case was also evaluated. The results were carried over to prototype and to optimize the process.

Jan 1, 2003

By E. Fregeau-Wu

The mineralogy and grain size distribution of phases in a steelmaking slag and experimental products from the heating of the slag under various conditions were determined to explore the possibility of recycling of the iron and manganese to the blast furnace. The steelmaking slags consisted of three major phases: dicalcium silicate, dicalcium ferrite, and Mg-Mn-wustite. Most of the phosphorus was contained in the dicalcium silicate and to lesser extent in the dicalcium ferrite. Due to the fine grain size of the dicalcium silicate, grinding and magnetic separation required pretreatment to increase the grain size and hence the liberation. Experiments on a steelmaking slag were conducted by heating the slag to 1633-1748°K( and slow-cooling in an inert atmosphere at various rates with or without the addition of fluorspar (CaF2) as a flux. Grain size distribution analyses of the starting material and the slow-cooled products were performed using the SEM-IPP area scan method and the QEM*SEM linear scan method. Comparable and reproducible results were obtained on the same sample using both methods. A size versus volume percent plot showed the increased grain growth most effectively. Examples of the grain size distributions obtained were used to show that a higher soaking temperature prior to slow-cooling, a slower cooling rate, and the addition of fluorspar to the slag promoted grain growth.

Jan 1, 1989

By T. Sakaguehi

Some attempts were made to recover and remove of uranium that may be present in refining effluents, mine waste Water, and other waste sources by using microbial biomass. To establish which microorganisms accumulate the most uranium, 135 species of microorganisms (42 bacteria, 26 yeasts, 34 fungi and 33 actinomycetes) were screened. Of these 135 species of microorganisms tested, extremely high uranium absorbing ability was found in Pseudomonas stuzeri, Neurospora sitophila, Streptomyces albus and Streptomvces viridochromogenes. In addition to the research on uranium uptake, thorium recovery by using microorganisms was investigated. High abilities were found in Streptomyces levoris and Bacillus subtilis. The selective accumulation of heavy metal ions by various microorganisms has also been examined. Uranyl, mercury and lead ions were readily accumulated by almost all of the species of microorganisms tested. Actinomycetes and fungi differ from many bacteria and most yeasts in their selective accumulation of uranium, and mercury. The basic features of uranium uptake by Streptomyces viridochromogenes, a microorganisms with high uranium-uptake ability, were investigated systematically. Synthesizing these results, we suggested that the accumulation of uranium into these microbial cells is not directly mediated by any metabolic process:, but almost completely dependent upon physicochemical adsorption on the cell components. In addition to this fundamental research, uranium recovery was investigated in immobilized Streptomyces viridochromogenes. These immobilized cells adsorbed, uranium readily and selectively. The immobilized cells recovered uranium almost quantitatively and almost all uranium adsorbed was desorbed with 0.1 N Na2CO3, These results showed that microbial cells are more stable after Immobilization and can be used repeatedly for the process of uranium adsorption-desorption. These results suggested that these microbial cells can be used for the recovery and removal of nuclear fuel elements, such as uranium and thorium, from refining effluents and mine waste water.

Jan 1, 1991

By V. I. Lakshmanan

Crown ethers are gaining importance in separation technology specifically for rare earth elements (REE, La to Lu plus Y) and precious metals (Au, Ag, Pt, Pd, Rh and Ir) due to their specific binding ability, metal complex stability and high extraction efficiency. The selectivity of crown ethers in extraction of these metals depends on different factors, including the cavity diameter and nature of a donor atom of the crown ether, size and charge of the metal ion, diluents and counter ion. Demand for strategic REE and precious metals are consistently increasing in the world while the separation of these metals is most challenging tasks. In this paper, the use of crown ethers in separation of REE and precious metals, reaction mechanisms and simplified process flowsheets will be elucidated. New reagents with high selectivity for the separation of these metals are further expected to produce high purity metals.

By Saeid Pournaderi, Ahmet Geveci, Ender Keskinkilic, Yavuz A. Topkaya

"This study investigated calcination behavior of one of the Turkish laterite deposits, which was recently found in Sivrihisar region. Representative limonitic laterite samples (1.26% Ni) taken from Yunusemre Karasivritepe and Kucuksivritepe location were first subjected to drying. Removal of chemically bound water and other volatiles were then studied, in detail. In the calcination experiments, temperature and time were the main experimental variables. Thermal treatment was conducted at the specific temperatures in 250 °C - 800 °C range. The weight losses due to elimination of chemically bound water and other volatiles were reported to be approximately 10 per cent of the weight of the ore. For the particle size used in the current work, 700 °C and 40 minutes were determined to be the optimum calcination temperature and time, respectively.IntroductionThe nickel ores that are economically valuable can be grouped into two categories: sulphide type nickel ores and oxide type nickel ores, namely laterites. Over all reserves in the world, 40% are sulphide nickel ores and the remaining 60% are laterites [1]. Pyrometallurgical nickel extraction from sulphide type nickel ores is conducted via matte smelting. More recently, laterite ore bodies have been subjected to nickel extraction. Depending mainly on the chemical composition of the laterite and the process economics, various extraction techniques have been implemented: pyrometallurgical route involves ferronickel smelting. High pressure acid leaching (HPAL) is the commercial method for hydrometallurgical nickel extraction, while ammonia leaching (CARON Process) is a combination of pyrometallurgical and hydrometallurgical processes [2]. With the improvements in these processes, it is predicted that laterite’s share in the world nickel production will rise to 50% in 2012, while it was reported to be 42% in 1,200,000 tons of annual production in 2003 [3]."

Jan 1, 2011

By Vladimir Panjkovic, Ostrovski. Oieg, Campbell Cripps Clark, John Truelove

"Effects of properties of raw materials and blast on the performance of an iron bath reactor have been examined by a mathematical model. The model consists of three modules: 1) chemical reactions in the gas phase and heat transfer from gas to droplets ejected from the bath; 2) heat losses from the vessel and radiative heat transfer from the freeboard to the bath; and 3) heat and mass balances for the bath. The following parameters of the process are calculated: coal, ore, flux and oxygen consumption, post-combustion ratio and heat-transfer efficiency, temperature and composition of the off-gas, and slag and metal chemistry.IntroductionOne of the anticipated advantages of smelting reduction over conventional ironmaking is the use of lower-grade raw materials. In this work, the effect of-properties of raw materials on the performance of an iron-bath reactor is examined with a numerical model. The model is also used to assess the effect of properties of the blast (flowrate, temperature and oxygen enrichment) and ejected droplets (generation rate, size and ratio of total weights of slag and iron droplets) on the key parameters of the process. In the process coal, oxygen, ore (which may be partly prereduced) and fluxes for specified slag composition are charged to the bath. Slag and iron droplets are ejected from the bath into the gas phase, where they are heated before returning to the bath. Iron droplets undergo decarburisation and reoxidation with CO2 and H2O. Dust is also generated from the bath, and oxygen or preheated air for post combustion is injected from the top of the vessel.The model consists of three modules: 1) reactions in the gas phase and heat transfer from gas to droplets ejected from the bath; 2) heat losses from the vessel and radiative heat transfer from the freeboard to the bath; and 3) heat and mass balances for the bath. The structure of the model and the data exchange between the modules are shown in Fig. 1. The following parameters of the process are calculated: coal, ore, flux and oxygen consumption, postcombustion ratio (PCR), heat transfer efficiency (HTE), off-gas temperature and composition, slag and metal chemistry, and rates of decarburisation and reoxidation of the iron droplets."

Jan 1, 1996

By Djona M. Gaballah I.

Selective chlorination of unroasted and roasted spent hydrorefming catalysts was studied between 300 and 600°C using the following gas mixtures : C12+CO, C12+N2 and CI2+air. Such materials contain Co, Ni and Mo compounds supported by alumina and/ or silica. They also contain variable amounts of V compounds, C, S, etc., accumulated during the life time of the catalyst. Direct oxychlorination of the C+S rich sample allows higher extraction rates than those obtained by the carbochlorination of the same roasted one. It seems that the roasting step doesn't favor the economic metals' recovery. Results of the chlorination of C+S poor spent catalysts, in the presence of CO, in the chlorinating gas mixture, or of carbon added to the sample, were comparable. Cobalt and nickel chlorides were .extracted from the chlorination residues by their dissolution with acidified water, whereas molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The recovery rates of valuable metals as well as the selectivity were higher for the chlorination of spent catalysts than results obtained by the hydrometallurgical processing of the same sample. Results of the scale-up of the oxychlorination of the unroasted sample confirmed those of the laboratory scale. The global recovery rates were about 88 pct of cobalt, 93 pct of molybdenum and 76 pct of vanadium. The carbochlorination was applied to the recovery of W and Ti from Denox catalyst that is a carbon and sulfur free one. Recovery rates higher than 99 pct at temperatures lower than 500 °C could be obtained. This may indicate that the chlorination process can be applied to the treatment of various industrial wastes or by-product containing transition and/or refractory metal compounds A flow - sheet for the pretreatment of these materials is proposed.

Jan 1, 1995

By Hong Yong Sohn, Miguel Olivas-Martinez, Zhixue Yuan

A novel flash ironmaking process that directly reduces iron oxide concentrate particles by gas is under development. The goal of this work was to study the possibility of reoxidation of iron particles in various gas mixtures. As the product iron cools down in the lower part of the flash reactor, conditions may become favorable for reoxidation because of equilibrium and high reactivity of iron particles. The effects of temperature (823 – 973 K) and H2O partial pressure (40 – 100 pct., Ptotal = 86.1 kPa) on the reoxidation rate were examined. The pressure dependence was first order with respect to water vapor, and the activation energy was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed. For oxidation in O2-N2 mixtures, the effects of temperature (673 – 873 K) and O2 partial pressure (5 – 21 pct., Ptotal = 86.1 kPa) were determined. Reoxidation in pure CO2 was also investigated at 873 – 1073 K for comparison.

Jan 1, 2014

By P. N. Anyalebechi

The effects of Si (0.19-0.52 wI. %), Fe (0.20 wI. %-0.44 wI. %), and Cr (0-0.10 wI.%) on the response of ingots of aluminum alloy 3004 solidified at different rates (O.IO°C/s to 30°C/s), to homogenization heat treatment have been investigated. Response to homogenization was determined by quantifying the following microstructural parameters: (i) amount of Mn retained in solid solution; (ii) types, relative amounts, sizes, size distributions, shapes, and chemical compositions of second phases; (iii) extent of the alpha-transformation (i.e., AI6(Fe,Mn) --7 (XAI12( Fe,MnhSi) reaction; (iv) dispersoid formation; and (v) alleviation of dendritic microsegregation. Of the three alloying elements investigated, Si had the greatest effect on the response of aluminum alloy 3004 to heat treatment. Increase in Si content, fineness of cast microstructure, and homogenization temperature facilitated alpha-transformation reaction, dissolution of Mg2Si, loss of Mn supersaturation, and formation of AldFe,Mn)3Si and Mg2Si dispersoids.

Jan 1, 2008

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By J. L. Holman

The Bureau of Mines is investigating recovery of Ni, Co, Cr, and other metals from mixed contaminated supera110y scrap. The scrap is melt-refined and cast into anodes for electrodeposition of recyclable Ni-Co alloy. Melt oxidation using roasted superalloy grinding sludge as oxygen source can divert the Cr to the slag but with excessive Ni-Co loss. Melt oxidation-carburization or direct melt carburization retains -95 pct of the Ni-Co in the anode alloy. With direct carburization, -90 pct or more of the Cr and other refractory metals report to the anode alloy, largely as carbide phases insoluble in electrolysis. Electrorefining data relate parameters such as controlled cathode potential, Fe and Cr impurities, pH, and compartmented cell use, to current efficiency and Ni-Co deposit quality. Recovery of -90 pct of the Ni-Co in the scrap can be achieved. Preliminary experiments to recover Cr, W, and other metals from the anode sludge and other byproducts are discussed. 347

Jan 1, 1987

By Michael L. Sorokin

The behaviour of cobalt during processing of nickel raw material is analysed within the Ni-Co-Fe-S-O-SiO2 system using the computer model. For this purpose the thermodynamic parameters for "three-suffix" Margules's equations in Co-Fe-S and Co-Fe¬Ni-O-S1O2 systems were computed! Phase and iso-activity diagrams for Co-Fe-S system, and phase diagrams for the systems Co-O, Co-Fe-O, Co-Ni-O, C-oO=SiO2 and Co-Fe-O¬SiO2 are calculated using the developed computer programs and identified parameters. The diagrams are used to analyze cobalt behaviour at smelting and converting.

Jan 1, 1995

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.

Jan 1, 1996

By Albert Wraith, Thomas Price, Wayne Boyd, Skip (I. E. ) Hills, Cameron Harris

Most Peirce-Smith converters inject air through tuyeres, with nitrogen representing the majority of gas passing through the process. The nitrogen controls the temperature of the vessel by carrying away heat from the reactions, both globally and locally at the tuyere tip. However, nitrogen adds energy to the bath and contributes to splashing and limits the blowing rate. High oxygen smelting has made streams of gas containing high concentrations of sulphur dioxide commonplace, which can be used to substitute SO2 for nitrogen and drastically changes Peirce- Smith converting (and all other smelting/converting processes as well). Less SO2 is required to carry away the same quantity of heat, which allows higher concentrations of oxygen and leads to the possibility of increased production. The paper investigates this substitution, its impact on converter productivity, and on the remainder of the plant. 181

Jan 1, 2009

By Sui Xue

A process has been developed from laboratory-scale experiments for the aqueous processing of various lead-bearing wastes. The process exploits the limited solubility of lead in sulfate-rich solutions to effectively separate lead from other metals. The lead sulfate is then completely converted to lead carbonate using sodium carbonate and ammonium carbonate. The effectiveness of this conversion was observed to be sensitive to the solution pH and carbonate concentration. The final stage of the process uses low temperature calcination of the lead carbonate to form PbO. Yellow lead oxide (massicot) is readily formed if calcination is conducted at a temperature at or iibove 50G°C, wlule red iead oxide (iitharge) is formed at temperatures near 450°?C. A complete economical analysis of the process will be discussed.

Jan 1, 1996

By A. Kar

A mathematical model is presented for pure titaqium deposition from titanium tetrabromide on a stainless-steel (SS 304) substrate. Five three-dimensional, transient, and nonlinear partial differential equations are used to account for the diffusion of various species inside the deposition chamber and the thermal decomposition of titanium tetrabromide, titanium dibromide, and titanium monobromide at the surface of the substrate in order to determine the thickness of the titanium film deposited on the substrate. The effects of various process parameters on the deposition and shape of titanium films are examined, and under certain conditions, the deposited titanium films are found to have volcanic profiles.

Jan 1, 1992

By Zbigniew Zurecki

The selection of atmosphere composition is critical for controlling surface quality of reactive aluminum alloys during solution treatments. An improper selection of annealing atmosphere can result in surface blistering in AI-Mg and sub-surface depletion of lithium in AI-U ingots. To determine optimum atmosphere compositions for homogenizing A1-Mg and Al-Li alloys, Ii number of exploratory experiments were carried out in air, nitrogen, and carbon dioxide based atmospheres including reactive impurities or additive such as moisture and sulfur hexafluoride. This paper describes the influence of these atmospheres on high-temperature oxidation and sub-surface defects. The results are discussed in terms of the change in Pilling-Bedworth ratio.

Jan 1, 1996

By A. E. M. Warner

In co Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003