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By Singareddy R. Reddy, Ramana G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. An expression for the activity coefficient of a dilute solute, 2(oxygen), in a binary solvent 1-3 is derived. It is used to calculate the logarithmic activity coefficient of oxygen in Pb-O-Gu, Pb-O-Bi, AgO- Sn, Pb-O-Sn and Ag-O-Pb metallic systems. Self interaction parameter of the solute is derived from the partial Gibbs energy of solute using constant compositional path. The derived equation is used successfully to deduce the self interaction parameter of oxygen in Pb-O-Gu and Pb-O-Bi metallic systems. The predicted thermodynamic parameter data i.e activity coefficient and self-interaction parameters are in an excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionThe nature of solute interactions such as oxygen, nitrogen and sulfur with the metallic solutions are important for a number of chemical and metallurgical processes. Several theories [1-23] have been developed to evaluate fundamental thermodynamic properties of solutes constituting two elements. The activity of solutes has been calculated using statisticalor quasi- chemical approach.Wagner's [4] Ideal Solvent Model is based on one energy parameter to describe the compositional dependencies of the activity coefficient of nonmetallic solutes such as oxygen in binary metallic solutions. This model depends on a constant energy of interaction for the exchange of atoms from the coordination shell of an oxygen atom to the shell of an interstitial site and cannot account for properties of strongly interacting systems [4]. Therefore, several attempts have been made to improve the Wagner's model for the strongly interacting systems. [10-16]."

Jan 1, 1996

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. In this work, thc potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (DW). Seven taxa are of Alyssum genus and one of Bornmuellera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mglkg or 2.5%) and Alyssum markgrafli O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By den Bulck A. Van

In Europe, 50% of the copper originates from recycling. High-Cu containing scraps are regularly rich in impurities like Fe, Ni, Sn and Pb. Many high-Cu containing scraps are fed directly into anode-furnace casting installations or furnaces with limited refining capability. The impurities levels of the anodes produced in these processes should however remain acceptable for further electro-refining. The distribution of Sn between copper and slag has been investigated for conditions relevant to copper converting. Unlike previous studies, this work focuses on the behavior of Sn relevant to fire refining conditions, which are essential for anode refineries.In this study, liquid Cu–1Sn and CuOx–FeOy–SiO2 slag, with CaO additions, were equilibrated at 1300 °C in vacuum sealed SiO2 ampoules. After metal–slag equilibration, the samples were quenched in water. The composition of the slag and Cu metal was investigated with Electron Probe X-ray Microanalysis. The distribution coefficients of Sn between slag and Cu metal were determined as a function of slag composition.

By Y. Z. Zhang

Cyanide has generated environmental concerns because of its toxicity, and it may not respond to the treatment of complex and refractory gold ores. Gold leaching by thiourea is one of the most promising substitutes of cyanide. However, the high reagent consumption has hindered thiourea from its commercial application in gold extraction. The process chemistry and mechanism of thiourea degradation has been discussed on the basis of chemical bonding theory, thermodynamics and electrochemistry in this paper. Progresses on the decreasing of thiourea consumption have been summarised. The potential application of thiourea in gold extraction has been evaluated.

Jan 1, 1996

By Takahiro Furuzono

Saganoseki Smelter and Refinery of Pan Pacific Copper Co., Ltd. started treating copper anode slimes using a unique hydrometallurgical process in chloride media in 1997. The process comprises the following stages, decopperizing, wet chlorination, solvent extraction for gold, silver chloride reduction, and separate reduction stages that treat the gold extraction raffinate with sulfur dioxide gas. Precious metals and rare metals in the copper anode slimes are dissolved in an aqueous solution of hydrochloric acid by oxidative leaching, which is termed wet chlorination. Gold is efficiently extracted from the chlorination liquor by dibutyl carbitol in the solvent extraction stage. Gold is reduced by oxalic acid from goldloaded dibutyl carbitol and recovered as gold powder. The gold powder is cast directly into granules or ingots of more than 99.99% purity without electrorefining. Selenium is recovered as a selenium residue by reduction with sulfur dioxide gas and refined through vacuum distillation. The plant was designed to process 132 tonnes of copper anode slimes per month and has a current capacity of 206 tonnes per month due to several enhancements. Compared with the conventional process, the hydrometallurgical process described here provides some advantages, in particular, a higher product quality, shorter gold-retention time, and reduction in environmental load.

By E. Oshima

The only one reverberatory furnace smelting in Japan has been alive in Onahama Smelter, Onahama Smelting and Refining Company. The fuel for the reverberatory furnaces had been changed from bunker C-oil to mainly coal and partially waste tires to reduce the energy cost. The steam, recovered by the waste heat boilers of the reverberatory furnaces, has been utilized fully for the power generation to save the purchase power. Copper concentrate has been smelted also by injection through tuyeres in the P.S. converters since 1983. The amount of concentrate, treated in the converters, was increased by the construction of small oxygen plant in December, 1990. In the paper, the current practice and improvements in the reverberatory and converter operations are described.

Jan 1, 1993

By F. Patisson

During exothermic gas-solid reactions, heat generation makes temperature rise and modifies the rate of the various mass transfer processes, namely the chemical reaction itself, the pore diffusion and the external transfer. We have investigated this thermal effect during the oxidation of zinc sulfide porous pellets in a thermo balance furnace, between 550 and 900°C-and under O2-N2 atmosphere. The results have been' analyzed by using, firstly, the law of additive reaction times derived from the isothermal Grainy Pellet Model, and, secondly, a new numerical model taking into account non-isothermal conditions. Both the models can satisfactorily simulate conversion versus time, but the numerical model also depicts the temperature evolution within the pellet. Finally it is shown that owing to the heat generation the zinc sulfide oxidation takes place under diffusion control (3/4 internal, 114 external) in all the cases studied. During the course of reaction, the. pellet undergoes strong temperature variations, with thermal gradients confined to a shell oxide layer.

Jan 1, 1996

By Liangying Wen, Feng Xia, Chenguang Bai

"The situation of the Ti-V-Magnetite samples reduced with microwave has been investigated in laboratory. Firstly, the paper focuses on the heating behaviors of vanadium-titanium magnetite and characteristics of carbothermic reduction of V-Ti-magnetite in the microwave field. The effect of concentrate's size, quality on heating behaviors and reduction processes were researched. Results show that microwave heating may be a new heating resource replace of carbonic combustion reaction in reducing reaction. When the allocation of carbon is (16.7-30)%, carbothermic reduction of V-Ti-magnetite in the microwave field can proceed; with the increasing of carbon mixed, the metallization rate increases; and Fe, V can be reduced from their oxides in the microwave field; Titanic low oxide can be reduced from TiO2.1. IntroductionThe resource of Ti-V-Magnetite is abundant in the western area of Panzhihua in China, so far a mineral deposit of 4.64 billion tons have been proved up, it contains 14.75 million tons of V2O S which accounted for 87% of the vanadium and 5.93 hundred million tons of TiO2 accounted for 94% of the titanium resource respectively in China. The previous study proved that the major composition of mineral of the Ti-V-magnetite are Ti-magnetite, limonite, iron spinel, magnesium spinel etc, and the main elements of the Ti-V-magnetite in this area are Fe, Ti, V, Cr, Co, Ni, Ga, Sc etc[1] Due to the restrict of the BF-BOF process technical, during the smelting of the iron, the level of extracting the vanadium, titanium as well as other metal elements is limited. This results serious wasting of resources. To develop a new reduction process of Ti-V-magnetite is on the agenda, the microwave assistant reduction could meets this need, based on its characteristic of easy controlling of heating rate. To make use of the microwave energy to substitute the released heat sources of carbon combustion with air, use the solid phase state reduction at a relative lower temperature, make the beneficial element in Ti-V-magnetite transferred into the metal phase, then separated from the impurity. It is well worth to point out that once the microwave based reduction method has its industrial scale, it will take an outstanding position by its less release of carbon dioxide. This new environment-friendly process will play a vital role in the development of social industry and economy."

Jan 1, 2008

By Giacobbe Braccio, Alessandro Blasi, Assunta Romanelli, Massimo Morgana, Corradino Sposato

Yttrium is a strategical material for its several usages in a wide range of industrial production. For this reason, improving the recovery of Yttrium has become a crucial focus for international research. In this scientific activity, the utilization of two extractants, 2-ethylhexyl-mono 2-ethylhexyl ester phosphonic acid (P-507) and sec-octylphenoxy acetic acid (CA-12), working in a synergistic extracting system, has been tested. A series of trials have been carried out to optimize the experimental conditions in order to separate yttrium from a mix of heavy rare earths in chloride media. Tests with different relative concentrations of extractants and a phase modifier (TPB, trybutyl phosphate), with different presaponification rate, have been performed to evaluate the behavior of the synergistic system. Results are very promising to recover and separate yttrium with a high purity.

Mar 1, 2017

By W. K. Choi

Stainless steel exposed to wet environments at ambient temperature is subject to the formation of a surface biofilm. Depending upon the prevailing environmental conditions (dissolved oxygen, pH, Eh, concentration of cationic/anionic species), the biofilm may stimulate corrosion through formation of differential aeration zones and concentration cells. Corrosion significantly impacts the United States economy, since on a yearly basis, corrosion induced losses are estimated to be over $200 billion. A large portion of this corrosion is imputable to bacterial activity, and basic information is needed for a better understanding and control of the biocorrosion phenomenon. The present study has investigated the influence of Thiobacillus ferrooxidans in the corrosion of American Iron and Steel Institute (AISI) 304, 316 and 416 stainless steel samples. The formation of biofilm and microstructural changes on the surface of stainless steel samples and their weldments were assessed by microscopic examination, and the changes in the mechanical properties by stress-strain measurements. The significance of the results will be discussed.

Jan 1, 1993

By R. Nilsson

In the present work, an assessment of the sulphide capacities of a number of binary and ternary slag systems have been carried out in the light of a sulphide capacity model. The model is based on the expression: {CS- exp (-A G °/R T) ? ao2 / fs2-} where AGO is the standard Gibbs energy change for the above reaction, ao2 is the activity of oxygen ions and f, is the activity coefficient of the sulphide ion in the slag. In the present model, the ratio (ao2/fs2) is optimized for the experimental data available in literature. The systems assessed are the binaries MnO-SiO2, CaO-SiO2, Al2O3-CaO, as well as the ternaries CaO-Al2O3-SiO2 and CaO-MnO-SiO2. In the case of all these systems, the experimental data available in literature were complemented by measurements carried out at the Division of Theoretical Metallurgy. The sulphide capacities of some FeO- containing binary, ternary and quaternary slags are also examined. The potentiality of the model to estimate the sulphide capacities of complex slag systems from binary and ternary data is demonstrated.

Jan 1, 1996

By P. D. Lee

The effect of strontium on porosity formation in aluminum-silicon alloys is not well understood and there is no consensus upon the cause of the effects observed. This paper describes a series of experiments where the effect of adding strontium on pore formation was observed directly with combination of a traditional temperature gradient stage and real time micro-focus radiography. These in situ observations provide a new insight into the effect of strontium on the nucleation and growth kinetics of porosity. The addition of strontium was found to have a minor effect on the growth of the pores in the mushy zone. However, strontium appeared to alter the nucleation and stability of hydrogen bubbles within the melt. The interaction of strontium with titanium-boride grain refiners produced an even stronger change in the nucleation and stability of the bubbles formed.

Jan 1, 2002

By Liu Wei-feng

In this paper, the practice of separating precious metals from base metals in gold-antimony alloy by selective chlorination leaching under controlling potential in China has been introduced in detail. The precious metals and the base metals can be separated completely when the complex gold-antimony alloy is treated by this process. The impurity metals were removed effectively since the leaching efficiencies of copper, nickel and antimony are over 99%, with direct recovery of gold being 99.83% that is about 20% higher than that of the original process and silver, antimony, copper and nickel are also recovered effectively. The gold grade of the resulting crude gold powder can reach to 94%.The new process has been applied in the treatment of gold-antimony alloy for two years, and many former procedures have been cancelled, such as electrolysis, Anode slime leaching by nitric acid, smelting in crucible and blowing in muffle. The new process is more shorten, lower cost and friendly to the circumstance comparing to the original process.

Jan 1, 2008

By Atsuhiro Nabei, Ken-ichi Yamaguchi

"Wet chlorination process of de-copperized anode slime is followed by de-chlorination stage in which lead-sulfate and metallic silver form silver residue. The silver residue is subsequently reduced to Ag2Se matte and PbO-SiO2 slag to remove lead to the slag in a short rotary furnace. Although this smelting process is proven well in actual operations, few papers have investigated its metallurgical aspects. This paper will describe the effectiveness of controlling parameters adopted at the Naoshima Smelter & Refinery and discuss the decisive factors influencing silver loss to PbO-SiO2 slag.IntroductionThe precious metals plant at Naoshima smelter & refinery was established in 1989, and has produced electrolytic silver, refined gold and platinum-group metals (PGM) from de-copperized anode slime as by-products of electrolytic copper. The process for gold production has been innovated from conventional smelting process to hydrometallurgical process since 2004 [1], while the process for silver production has still remained the same.The process for silver production at the Naoshima smelter & refinery is illustrated schematically in Figure 1. De-copperized anode slime is, at first, concentrated in the froth flotation process, then leached in the wet-chlorination process, and converted to silver residue in the de-chlorination process. The silver residue, which is a mixture of lead-sulfate and metallic silver, is charged to a short rotary furnace for the oxidation roasting to volatilize selenium dioxide and subsequent reduction smelting. In the smelting stage, silver residue and reverts containing selenium are smelted with flux and carbonaceous materials to form PbO-SiO2 slag and Ag2Se matte. Furthermore, Ag2Se matte is transferred to a rotary cupell and oxidized by air with the addition of sodium carbonate and sodium nitrate to produce silver anodes while removing impurities into litharge. Silver anodes are electrolytically refined by the Moebius process. Electrolytic silver is washed, dried and, finally, cast into 30kg-bars."

Jan 1, 2011

By K. S. Barros, D. C. R. Espinosa, J. A. S. Tenório

Over the past several decades, electrodialysis membranes have been employed for the removal of metals from galvanizing industry effluents. However, for its technical viability, it is useful to know some properties of the system to avoid, for example, precipitation of inorganic salts, destruction of the membrane and an increase in the energy consumption. The scope of the present study is to use chronopotentiometry to determine limiting current densities, transition times and resistances of the cationic membrane HDX 100 using a synthesized solution of the galvanizing industry effluent prepared with copper sulfate and sulfuric acid in different concentrations: 0.1, 0.5 and 1.0 g/L of Cu +2. The current-voltage and chronopotentiometric curves obtained have clearly defined regions and it was verified that the Cu+2 concentration causes a significant increase in the limiting current densities and in transition times. However, a high decrease in resistance occurred because at the highest concentrations, it is more difficult to reach the zero concentration value at the membrane surface. Besides, the pH increase causes a significant decrease in the limiting current density and in the transport number, but a slight increase in the resistance due to the presence of hydrogen. The results obtained confirm that the chronopotentiometry method is a valuable tool to determine membrane properties.

Mar 1, 2017

The high pressure acid leach process (HPAL) is being commercially used in four plants around the world to treat limonitic laterites. The two major operating costs of the HPAL process are the sulphuric acid and the energy required to heat the pulp to the desired temperature (>240°C). As an alternative to acid injection and steam heating, the in-situ generation of sulphuric acid and heat, produced during the high temperature pressure oxidation of sulphur-bearing materials blended with laterites, has been investigated at the laboratory scale. Various sources of sulphur have been examined, in particular, elemental sulphur, pyrrhotite and a Cu-Ni low-grade bulk concentrate. Under the proper blend ratios, all sulphur sources tested generated sufficient acid to result in equivalent nickel and cobalt dissolutions. A significant improvement to the process economics can result from the addition of sulphur sources containing valuable by-products, such as nickellcobalt andlor precious metals (gold and PGMs). This is especially true in the latter case, when the HPAL can be operated under Platsol conditions (i.e. with the addition of 5-10g/L of chloride), to dissolve the base metals and precious metals simultaneously in the autoclave. Various examples of the application of this concept are presented, together with a brief discussion of its implication on the autoclave design and the downstream processes to recover the values from the leach solutions. Keywords: limonite, co-treatment, acid consumption, sulphur, sulphur compounds, pressure acid leach (HPAL, PAL), Platsol process

Jan 1, 2004

By E. J. Peuraniemi

Primary copper production using suspension smelting techniques like Outokumpu Flash Smelting always causes some dust formation. Flue dust particles are formed when sulphide feed material reacts violently with oxygen inducing particle disintegration and total desulphurisation of fragments. In the process, flue dust follows the off-gases to the heat recovery boiler (HRB) where its sulphation takes place because of prevailing conditions. Sulphation releases heat and causes also a drop in particle melting temperature and, further, particle sticking to the walls and heat exchange tube banks. Sulphation of synthetic CU20 particles were examined using a laboratory scale fluid-bed reactor. This study aims to a better understanding of flue dust behaviour in a HRB and, thus, to a better operational practise and design of a HRB. The effect of PSO/PO2 -ratio and temperature on the sulphation kinetics were tested. Standard chemical analysis, light optical and scanning electron microscopy with energy dispersive spectroscopy were used to examine the samples.

Jan 1, 2001

By D. Bruce Wilson

The reaction of oxygen and solid aluminum produces the well-known surface coating of aluminum oxide, Al2O3. Thermodynamic properties and kinetic mechanisms of this reaction are extensively documented. Less well-defined are the corresponding liquid phase reaction and reactions which would be characterized. as 'burning' of aluminum. This paper reviews the solid aluminum-oxygen reaction as a foundation for discussing the flammability of aluminum in oxygen-enriched atmospheres. Appropriate thermodYDan3ic analysis and kinetic reaction mechanisms are developed. Available models of aluminum burning are reviewed and evaluated, The appropriate information for design of engineering applications of aluminum in oxygen atmospheres? is summarized.

Jan 1, 1996

By J. W. Lyman

The U.S. Department of the Interior, Bureau of Mines, investigated methods to recover valuable rare-earth materials from NdFeB magnet scrap. Although several processing techniques were evaluated" the best separation of rare earths from the NdFeB magnet ,scrap was obtained by sulfuric acid dissolution followed by precipitation of recyclable rare-earth salts. Both sodium and ammonium intermediate double-salt precipitates' that can be converted to a variety of useful neodymium products were investigated. The sodium system showed a neodymium recovery of 98 pct, while the ammonium system yielded 70 pct during double-salt precipitation. The iron-rich effluent following the rare-earth recovery was treated to produce sodium and ammonium iron jarosites that can be disposed of or converted to hematite. By following this new procedure, many materials handling and economic disadvantages found with fluoride or oxalate direct precipitation were avoided.

Jan 1, 1992

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of873 OK is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composItion formed under roasting of concentrates with particle sizes less than 0.02 J..lm (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CufeSz) each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forehamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003