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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 T. L. Baum

External oxidation during in-line heat treatment of TRIP steels can cause problems for the subsequent coating process. This research aims to elucidate the kinetic rates of internal oxidation, external oxidation and decarburization and their interdependence under different gas atmospheres and temperatures. A rolled steel sample chemistry of 0.14 wt.% C, 1.8 wt% Mn, 0.6 wt.% Si and 1 wt.% Al is used as a case study. Thermogravimetric techniques are used to examine the net mass change in a sample during heat treatment and the results show an initial mass decrease and later an increase for particular partial pressures of H2O. SEM-EDS, optical microscopy and glancing-angle x-ray are used to quantify the microstructure. The cross-section of the samples have 4 distinct zones: (i) an external scale, rich in fayalite, (ii) an internally oxidized region with Al, Si and Mn oxides in an Fe matrix, (iii) a decarburized steel region, characterized by large ferrite grains and low carbon content, and (iv) a relatively unaffected steel core with a structure similar to the starting material.

Jan 1, 2006

By Jeffrey W. Fergus, Shiqiang Hui

"Aluminum is an important alloying addition to the zinc used in the hot-dip galvanization of sheet steel to control the properties and appearance of the resulting coating. Optimization of the galvanization process requires control of the alloy concentration which can be improved through the use of chemical sensors. Aluminum sensors based on molten electrolytes are commercially available but are not widely used because of their high cost. One approach to reducing the cost is to use a solid electrolyte which can simplify the sensor design and thus reduce the cost of fabrication. In this paper, the development of an aluminum sensor based on a solid fluoride electrolyte, specifically magnesium fluoride, will be described.IntroductionThe concentration of the zinc bath used in hot-dip galvanization affects the galvanization process as well as the properties of the resulting coating. Thus, accurate in situ measurement of the alloy composition can be used to improve process control. This paper describes a solid-electrolyte-based aluminum sensor for monitoring the bath composition during hot-dip galvanization."

Jan 1, 1997

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 Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By S. J. Macnaughton

The Olympic Dam deposit in South Australia contains 2% copper and 0.06% uranium, which are present as bomite, chalcocite, chalcopyrite, uraninite, coffinite and brannerite. The copper is principally recovered using flotation. The flotation tailings, which contain the bulk of the uranium, and typically 0.3% copper, are leached using sulfuric acid and an oxidant at atmospheric pressure. This paper describes the results from a detailed investigation of the leaching behaviour of this ore. The influence of acid strength, Fe3+ concentration, redox potential and temperature on the dissolution of uranium and copper minerals was studied. Experimental data were obtained from extensive batch leach tests. Mineralogical studies, including SEM analysis of individual mineral grains, were also carried out. The maximum extraction of uranium determined experimentally was in good agreement with that predicted from SEM determination of the proportion of refractory brannerite in the ore. The leaching rate of copper was found to be independent of acidity over the range 20 g L-' to pH 2.0, but was strongly dependent on temperature and Fe3+ concentration. Uranium extraction showed a weak de endence on acidity, Arrhenius temperature dependence and a complex co-dependence on F>+ concentration and redox potential. A kinetic model has been developed, which predicts copper and uranium dissolution. This model will be incorporated into a more comprehensive model that can be used to predict leach performance and reagent consumption for specific ore samples.

Jan 1, 1999

By Ana E. Bohé, Georgina De Micco, Gastón G. Fouga

"In this work the reaction between several manganese oxides and chlorine is investigated in the range of temperatures between 650 and 950ºC. The reaction path for the chlorination of MnO is established, which involves recrystallization of high valence manganese oxides (Mn3O4 and Mn2O3) followed by its chlorination. For this reason, to understand the reaction of MnO, the chlorination of Mn3O4 and Mn2O3 has also been studied. The starting temperature for the reaction of these oxides is determined by non isothermal thermogravimetric measurements. The effect of temperature is analyzed, under our experimental conditions the rate of reaction is mass transfer controlled. The activation energy for the volatilization of manganese chloride is obtained which is in good agreement with volatilization enthalpy of MnCl2.IntroductionMany oxide ores which have manganese in their composition undergo chlorination processes during the extraction of refractory metals such as Ti, Hf and Nb. Although several works related with chlorination of manganese oxides were reported, there is no information about the kinetics or mechanism of the manganese oxide chlorination reactions. Okahara et al. studied the chlorination of manganese oxides and established that they react easily above 250ºC. Furthermore, they observed that chlorination of high order oxides is more difficult when there is not a reducing agent [1]. Ivashentsev studied the chlorination of manganese oxides using Cl2(g), CO(g) + Cl2(g) and COCl2(g). He established that the reaction of MnO started at 130ºC with formation of MnCl2(s), he also observed recrystallization of manganese sexquioxide [2]. Finally, the chlorination of manganese nodules from the ocean was studied by Murthy and Reddy [3] with the aim of obtaining valuable metals such as Mn, Co, Ni and Cu. They studied the influence of several parameters like temperature, carbon percentage, particle size and chlorine flow rate in the extraction process."

Jan 1, 2008

By Neng-Wen Yu, Miao Wang, Ji-He Wei

The mass transfer characteristic between powder particles and liquid steel in the RH-PTB (Powder Top Blowing) refining has been investigated in a water model of 1/5 scale for a 90t RH degasser. The sodium chloride powder with analytical purity has been used as the flux for blowing. The mass transfer coefficient of the liquid side has been determined under the conditions of RH-PTB process. The influences of the main technological and structural parameters on the mass transfer rate have been examined. The results indicated that under the conditions of the present work, the mass transfer coefficient on the liquid side increases with raising the lifting gas blowing rate, inner diameter of the up-snorkel, circulation rate of the liquid and particle size of powder flux. And it decreases with an increase in the inner diameter of the down-snorkel. It is in the range of (l.36-7.30) x 10·4 mis, the appropriate dimensionless relationships have been obtained as follows:

Jan 1, 2000

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 Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

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

"Alloying refining with rare earth elements followed by acid leaching was examined for the potential of upgrading of metallurgical grade silicon. Microstructure study of silicon alloyed with small additions of rare earths showed behavior relatively similar to the influence of calcium addition. After alloying with neodymium the phosphorus content was detected in various intermetallic silicides containing neodymium and iron. The content of lanthanum and neodymium in refined silicon was by several times lower than that of aluminium and calcium. Alloying with lanthanum and neodymium at smaller additions than calcium reduced the phosphorus content down to the same level. The efficiency of lanthanum and neodymium in removal of boron and phosphorus at the 1-2 wt% of their additions and their low solubility in silicon make the alloying with these metals followed by acid leaching an attractive option for the refining route of metallurgical grade silicon up to solar grade.IntroductionA striving for a cheap ""green"" energy directs the research interests in silicon solar cells towards new efficient refining routes for metallurgical grade silicon (MG-Si, -98% purity). The silicon price determines up to high extent the solar module's price, so that cheap and efficient metallurgical process is awaited. The research challenge is to fulfil the purity requirements of solar grade silicon (SoG-Si, 6N) by competing with the energy-consuming and environmentally unfriendly Siemens process. Most difficult impurities to remove are boron and phosphorus, so technologies dedicated to their efficient removal attract an attention of industry and academia.Alloying refining (also known as solvent refining) is one of the most promising refining options, which is based on a principle of solid-liquid extraction using limited solubility of impurity elements in solid silicon [ 1]. Various elements were proposed for alloying refining: aluminium [2], calcium [3], tin [4], iron [5], copper [6] etc. The attractiveness of the alloying refining is in decreasing a melting point of the metal mixture and an affinity of the alloying element to the most harmful impurities, especially to boron and phosphorus. However, the difficulties are still faced due to self-solubility of the alloying elements, their low affinity to boron and/or phosphorus, silicon losses and necessity of removal of the silicide impurity phases in an additional step, using acid leaching [7], fractional melting [ 8] etc."

Jan 1, 2013

By Randall M. Gennan

Generally sintering is focused on the bonding of particles at high temperatures; possibly with simultaneous densification. However, an important aspect of sintering occurs during heating at relatively low temperatures where polymer processing aids are removed via control of the atmosphere, heating rate, or hold time at intennediate temperatures. New insights into burnout processes show impact from the polymenype, particle size, amount of polymer, atmosphere, part geometry, and thermal profile. This presentation focuses on the key parameters to demonstrate improved mechanical property levels are available in traditional powder metallurgy alloys by proper selection of the processing polymer and proper care in its thermal extraction. The focus is on mechanical property, where gains up to 40% are demonstrated due 10 changes in the processing polymer. Further, atmosphere control during polymer burnout provides a benefit by allowing formation of desirable carbonitrides, giving strength levels over 3 GPa (over 400 kpsi). Insight is? gleaned from powder injection molding, where high polymer contents mandate proper processing control.

Jan 1, 1996

By Abbas H. Mirza

Arsenic and selenium are found in low quantities together with other metals in several nonferrous metallurgical process streams such as scrubber blowdown solution, acid plant wastewater, gas cleaning plant water, etc. Normally, the other metals in these streams are present as cations and can be precipitated by conventional lime treatment and sulfide polishing. However, arsenic and selenium are invariably present as anions, AsO33-and AsO43 in the case of arsenic and SeO32 and SeO42 for selenium. Conventional lime treatment removes most of the arsenic, but it does not remove selenium. The present paper reviews the processes and technologies developed to date on the removal of arsenic and selenium from metallurgical process streams.

Jan 1, 1996

By G. T. Lapidus, O. J. Solis-Marcial

"The oxidative dissolution of copper from refractory minerals, such as chalcopynte, represents a technological challenge that has occupied hydrometallurgists for more than half a century. Innumerable processes have been suggested, but the majority operates at high temperatures or employs corrosive media. The origin of this refractory nature is the formation of passivating phases of iron(III) or copper. One option is to add non-corrosive ligands that complex these metal ions, thereby facilitating their dissolution. In the present work, the effect of acetone in sulfuric acid solutions was studied. The initial experiments were on chalcopynte carbon paste electrodes using cyclic voltammetry, where greater reactivity was observed. Later, leaching tests with hydrogen peroxide, cupric sulfate and ozone and, as oxidants, were performed. High extractions were achieved in three hours at 50°C. The solid residues contained the iron in the form of Fe203 and FeOOH.IntroductionChalcopyrite is the most important mineral of polysulfide copper ores [1] and accounts for approximately 70% of the world's copper reserves [2]. Currently, the copper present in chalcopyrite is extracted mainly by pyrometallurgical processes, which generate environmental concerns because of the formation of SO2 gas and submicron particulates [3]. The development of a less aggressive hydrometallurgical process for the extraction of copper would constitute a possible solution to these problems. For that reason, studies of the dissolution behavior of chalcopyrite are of great technological importance [4], However, the proposed oxidative leaching routes for chalcopyrite, generally at high pressures and temperatures, have not been implemented on an industrial scale, because of the elevated costs required to equal the high copper extractions obtained in thermal processes. These extreme leaching conditions are required because of the refractory nature of chalcopyrite. Passivation has been used to explain this phenomenon, although researchers have disagreed on the composition of the layer, which is various have assumed to be sulfur, copper sulfides, and iron-bearing jarosites or hydroxides [5]. If the latter compounds are the cause, an alternative solution would be the use of polar organic solvents in the oxidative leach to decrease the formation of the passivating iron layer. In this work, the influence of acetone on the oxidative leaching of a chalcopyrite concentrate at room conditions is explored."

Jan 1, 2012

By Ker-Chang Hsieh

Four three-phase equilibria and one two-phase equilibrium in the FeNi- S-0 quaternary system in the vicinity of 1023 K and Pso2 = 1 atm were studied using the following emf cell 2 Pt,o2 (air)Zr02 .CaO/Pso2 = 1 atm, mixture of phases, Au The four three-phase equilibria are sp + (Fe,Ni )S + Ni 3s2, sp + Ni 3s2 + NiO, sp + NiO + N1S04 and Fe2 o3 + sp + (Fe,NOS04 -Y:he two-phase equilibrium is sp + (Fe,Ni)S. The two-.phase equilibrium was measured by using mixtures containing a major portion of one phase and a minor portion of the other. The results are presented in terms of oxygen potential as a function of YNi = nNi/(nN1+nFe) at constant temperature and pso2 = 1 atm. The stability diagram was also calculated using appropriate thermodynamic models for all the pertinent phases. The calculated diagram is in accord with the measured ones.

Jan 1, 1985

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 D. Raghavan

In recent years, the environmental issues related to the landfill shortage received considerable importance. Many polymeric solid wastes have high resistivity to chemical and biological degradation, and options are sought by which these wastes can be recycled and reused, or reduced in volume. The present study investigated the biodegradation of polyethylene by Aspergillus niger, and biodesulfurization of rubber by pure and mixed cultures of Thiobacillus thiooxidans and Thiobacillus ferrooxidans. The fungus, A. niger, was found to metabolize portions of polyethylene. Quantitative calorimetric measurements revealed that the amorphocity of the sample decreased during biodegradation. Removal of sulfur from synthetic rubber samples containing 2 to 15% sulfur, was studied in shake flask experiments and the associated oxygen consumption was studied in Warburg respirometers. The mixed bacterial cultures were more effective in the desulfurization of rubber samples than the pure cultures of T. thiooxidans and T. ferrooxidans. The data obtained in these studies may have far reaching consequence for the development of new effective processes regarding the remediation and management of discarded polymeric packaging wastes and car tire rubber materials.

Jan 1, 1993

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

Several processes are now available for the recovery of free and WAD cyanide from gold plant solutions and pulps. In the past, the incentive for evaluating cyanide recovery in gold plant flowsheets has been economic. In many cases, it has been possible to demonstrate (at least in the laboratory and on paper), an improvement in process economics by; (i) reducing the costs of tailings detoxification, (ii) recycling cyanide at lower cost than the purchase/delivery price of new cyanide, and (iii) generating additional revenue via by¬product sales. Despite these convincing arguments, few cyanide recovery plants have been built at operating gold mines. Also, there is arguably an even more compelling reason for mining companies to consider cyanide recycling. With the growing storm of negative public opinion that the use of cyanide in the mining industry is attracting - following several highly publicized spills over the last couple of years - the time has come for the gold industry to demonstrate environmental diligence and stewardship in the use of this commodity that is so vital for their industry. There is no doubt that the widespread implementation of cyanide recycling will reduce the impact of the cyanidation process on the environment, both by reducing the risk of spills (with less cyanide being transported from manufacturing plants to gold mines), and by reducing the loading of toxic and non-toxic metals and ions in the tailings. In this paper, the various processes that are available for cyanide recovery are discussed, along with the process chemistry. Results of several laboratory and pilot plant trials that have been conducted over the last few years are also presented.

Jan 1, 1998

By Songsong Wang

Recently, replacing Pierce-Smith converting process with the oxygen bottom-blowing continuous converting technology has become a new research focus. Based on the principle of Gibbs free energy minimization, the thermodynamic model of oxygen bottom-blowing continuous converting multiphase equilibrium system has been established. The elements distribution behavior is calculated at the same burden composition and operation parameters as the industrial production. The results show that the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in crude copper are 0.06, 0.0030, 0.070, 0.38, 0.39, 0.020, 0.017, 0.034, 0.010, respectively, and the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in slag are 0.53, 0.81, 0.020, 0.23, 2.5, 0.0048, 0.0010, 0.0030, 1.49, respectively. The calculated results agree well with the actual industrial production data, indicating that the model can be well applied in the oxygen bottom-blowing continuous converting practice.