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By Jaeheon Lee

Gold-copper alloys are shown to form during the cementation of gold on copper in a solution containing 0.25M [S2O32-] at 25oC. The alloy composition is strongly dependent on the initial Cu:Au ratio in solution and ranges from Au3Cu to AuCu3. XPS results for Au, Cu, S, and O are reported as a function of depth through an entire deposited film with an initial solution containing 20 ppm [Au] and 30 ppm [Cu]. The deposit contained about 20 atomic % gold and was predominantly Cu3Au. Underpotential deposition (UPD) theory is discussed as a mechanism for explaining the formation of these alloys. Several other systems that produce alloys during contact reduction/cementation are also discussed.

Jan 1, 2003

By Kazuteru Tozawa

Surface tension, density and viscosity coefficient of acidic copper sulfate solutions simulating electrolyte solution for electrolytic production of copper have been measured and are summarized as a function of the solution composition and temperature. Nickel sulfatc is taken to be a representative coexisting sulfate that affects the physical properties of the copper sulfate electrolyte solution. The sulfates in the solutions, including sulfuric acid, increase the physical properties under consideration. Gelatin, representing organic additives for electrolyte solution, was found to sensitively affect the surface tension of the solution at low concentration of up to 200mgIL. The surface tension was markedly lowered by the addition of gelatin and the increasing concentration of gelatin led to a more pronounced decrease in the observed values. The surface tension gradually increases with time after addition of gelatin and the increase is enhanced by higher acid concentration and higher temperature. The observed change in the surface tension is considered to reflect the preferential adsorption of gelatin to the bubble-solution interface and the decomposition of gelatin due to hydrolysis to form various molecules having smaller molecular weights.

Jan 1, 2003

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 Florian Kongoli

The production of a homogeneous self-fluxing sinter is an important step in iron making processes. A good sinter should have good permeability and reducibility and has to keep those characteristics for a certain time. An early melt down of the sinter in the blast furnace, where its solid state reduction is essential, would cause many problems such as low permeability and reductibility. Nevertheless, the important factors that influence these characteristics, such as the chemistry of the sinter and the fluxing effect during sintering and sinter reduction conditions have not yet been clarified. In today's new reality where many new minor components such as Al2O3 and MgO enter to the sinter through raw materials, the quantification of the fluxing effects during sintering becomes even more important. In this work, the liquidus surface and phase relations of the sinter primary melts in the CaO-FeO-Fe203-Si02 system at sintering conditions have been quantified. The fluxing effect of oxygen potential, Al2O3 and MgO has also been quantified by the means of some practical diagrams that can directly help the optimization of the sintering processes.

Jan 1, 2003

By Katsuyoshi Kondoh

The synthesis processing of Mg2Si or Mg2SiIMgO at lower temperature from the elemental magnesium alloy powder/chips and Si or SiO2 powder mixture was established via the repeated plastic working (RPW) based on Powder Metallurgy (PIM) process. RPW is much effective on the mechanical breakage of MgO surface films, which prevent from the solid-state reaction between Mg and Si powder. The solid-state synthesized Mg2Si particle of 200nm-2um is extremely fine, compared to that via the conventional casting process, causing the coarse one of 50-100um. This is because of not coarsening during the solid-state synthesis of Mg2Si. By using in-situ fonning process of Mg2Si via RPW and pre-heating before hot working such as extrusion and forging, the magnesium composite material with Mg2Si or Mg2Si/MgO dispersions was developed in employing Si or SiO2 particles, respectively. For example, when employing AZ31 chips as raw materials of the matrix, it has low density of 1.85g/cm3 and extremely superior mechanical properties, such as tensile strength over 350MPa with 5-10% elongation and Young's modulus of 47-50GPa, to the conventional Mg-Al-Zn alloys. The Mg composite alloy wires and pipes were produced via the hot extrusion process in the manufacturing plant, and also showed excellent mechanical properties.

Jan 1, 2003

By John J. Dunkley

Recent years have seen the increased use of hydrometallurgy in the smelting and refining of metals. However this is often used as a final refining step, following an initial pyrometallurgical smelting process. Huge amounts of material are produced as melts which have to be cast, comminuted, and taken up into solution or leached. A common method is to granulate the melt and then grind it. In the case of metallic melts this can be difficult or unfeasible due to the ductility of the granulated particles. Water atomisation is capable of replacing the granulation and grinding stages with a single process step that can process in excess of 30t/hour of melt into particles as fine as 50 microns. Applications in operation in Co, Cu, Ni, Ag, Au, Pt and Rh refining are discussed together with potential applications in copper smelting.

Jan 1, 2003

By Gerardo H. Achurra

During the last years, the Caletones Smelter, like others copper smelters in the world, has evolved from the conventional, inefficient, pollutant and expensive technologies, to modern, environmentally friendly and efficient ones. For this reason' as well as to improve its competitive position this Smelter shut down the reverberatory furnace, started up two big acid plants and has developed some pyrometallurgical technologies. The main facilities of the Caletones Smelting and Converting Process, in the present and the future, are the Teniente Converters, the reactors with a high operational availability that have reached concentrate top process capacities near to 2,400 tpd. These reactors operate in most of Chilean smelters as well as in other smelters in the world such as in Zambia, Peru and Mexico. Since 2000, the Caletones Smelting and Converting Process, has been adapted in two Teniente Converters, four Slag Cleaning Furnaces and four Pierce -Smith Converters. These facilities, together with the operation of two Fluidized Bed Dryers and two Oxygen Plants have allowed to reach concentrate smelting capacities and copper productions of 1,250 ktpy and 380 kfipy, respectively. Associated to EI Teniente Division Expansion Plan, Caletones Smelter, in the first stage, will increase its capacity to 1,440 ktpy in 2004. In the long term, Caletones has different options, such as the processing of 1,600 to 2,000 ktpy of concentrate, producing anodes, white metal or a mixture of them. These options are connected with CODELCO's Smelters & Refineries Strategic Plan, including Mejillones Project. The main challenges of Caletones Smelter are associated to the development and the consolidation of the Continuous and Environmental Friendly Processes, automation and control of different processes and to the improvement of its leadership between other Copper Smelters in the world.

Jan 1, 2003

By Fumitaka Tsukihashi

Phase diagrams of the CaO-SiO2-FeOx-MgO, Al2O3 systems are necessary for the analysis of copper smelting reactions and sintering process of iron ore. The effect of MgO and Al2O3 addition on the liquidus of the phase diagram of the CaO-SiO2-FeOx system at low oxygen partial pressure was observed. The liquid phase area changed by the addition of MgO and Al2O3 with a changing oxygen partial pressure from 10-8 to 10-3 atm (10-1 to 102 Pa) at 1573K. The effect of Fe3+/Fe2+ ratio on the melting mechanism is discussed.

Jan 1, 2003

By Qiu Dingfan

The Slurry Electrowinning Process (SEP) is a new hydrometallurgical method and clean technology, Sulfide ores can be treated by the SEP without S02 emission and the sulfur from the sulfides can be recovered in element form which is easy to stockpile and can be transported at low cost. In a special slurry electrowinning cell one can achieve at the same time the leaching of elements from the feed and the electrowinning of metals from the electrolyte, Because the anode reactions are utilized for leaching of some elements the consumption of the energy is decreased, SEP also has the advantage of separation some elements, It is especially suitable for treatment of complex concentrates containing Pb, Cu, Au, Ag and S, which could hardly be accepted by any smelter. In this work, the behavior of different metals in this process has been studied and it was found that the separation of metals in some minerals is possible through the SEP, Beijing General Research Institute of Mining and Metallurgy (BGRIMM) has studied the possibility of the SEP to treat bismuth concentrates containing S, Be and F in laboratory and pilot-test scale as well as in commercial plants, The commercial plant was set up in 1997, It has been in operation since that time, According to the results of laboratory experiments and pilot- plant test, a new plant to treat complex gold minerals was set up in 1998 and is in operation in 1999

Jan 1, 2003

By Jeffrey F. Adams

Gypsum fouling is a common problem in the hydrometallurgical industry. It is a particular problem in free sulphuric acid neutralization, or iron removal operations where sulphates are removed from aqueous solutions by the addition of calcium-containing bases. Previous work revealed a strong correlation between the degree of gypsum supersaturation in the reactor and the rate of scale growth indicating that scale formation and growth are primarily controlled by chemical phenomena. However, the chemical behaviour of gypsum is variable and unpredictable with solution chemistry and temperature. Many of the "rules of thumb" that are used to predict its behaviour (and avoid fouling) are in fact based on gypsum solubility in water, rather than on real mixed metal sulphate systems. However, despite this unconventional solubility behaviour, we have been able to accurately model it in Ni, Mg, and Zn containing solutions over a wide range of temperature (25°C-90°C) and solution concentration (0-6 m) using the OLI simulation software. Furthermore, by studying fouling rates in a simulated continuous neutralization reactor, the relationship between process conditions and fouling rates were explained for the first time. This has led to an understanding of how techniques for minimizing gypsum fouling work.

Jan 1, 2003

By Esher Hsu

On July 5, 1997, Environmental Protection Administration of Taiwan publicized the recycling regulation of waste home appliances that include four items, namely, television, refrigerator, washing machine, and air conditioner. It is believed that this regulation pioneers the law enforcement of waste home appliances in the world. The objective of this study is to provide helpful base for amending recycling rates of waste home appliances. This study investigates the collection and recycling costs of waste home appliances in accordance with these newly established routes and facilities, respectively. Cost survey was conducted among collectors and recycling plants of waste home appliances; consequently, the collection and recycling costs were analyzed, correspondingly. Results provide some suggestions regarding recycling route, recycling system, recycling rates paid by manufactures and importers, recycling subsidies to collectors and recyclers. Those suggestions may provide useful policy implications to EPA for the future decision-making regarding the recycling of waste home appliances.

Jan 1, 2003

By Philip L. Sibrell

A new process utilizing pulsed fluidized limestone beds was tested for the remediation of acid mine drainage at the Friendship Hill National Historic Site, in southwestern Pennsylvania. A 230 liter-per-minute treatment system was constructed and operated over a fourteen-month period from June 2000 through September 2001. Over this period of time, 50,000 metric tons of limestone were used to treat 50 million liters of water. The influent water pH was 2.5 and acidity was 1000 mg/L as CaCO3. Despite the high potential for armoring at the site, effluent pH during normal plant operation ranged from 5.7 to 7.8 and averaged 6.8. As a result of the high influent acidity, sufficient CO2 was generated and recycled to provide a net alkaline discharge with about 50 mg/L as CaCO3 alkalinity. Additions of commercial CO2 increased effluent alkalinity to as high as 300 mg/L, and could be a useful process management tool for transient high flows or acidities. Metal removal rates were 95% for aluminum (60 mg/L in influent), 50 to 90% for iron (Fe), depending on the ratio of ferrous to ferric iron, which varied seasonally (200 mg/L in influent), and <10% of manganese (Mn) (10 mg/L in influent). Ferrous iron and Mn removal was incomplete because of the high pH required for precipitation of these species. Iron removal could be improved by increased aeration following neutralization, and Mn removal could be effected by a post treatment passive settling/oxidation pond. Metal hydroxide sludges were settled in settling tanks, and then hauled from the site for aesthetic purposes. Over 450 metric tons of sludge were removed from the water over the life of the project. The dried sludge was tested by the Toxicity Characteristics Leaching Protocol (TCLP) and was found to be non-hazardous. Treatment costs were $43,000 per year and $1.08 per m3, but could be decreased to $22,000 and $0.51 per m3 by decreasing labor use and by on-site sludge handling. These results confirm the utility of the new process in treatment of acid impaired waters that were previously not amenable to low cost limestone treatment.

Jan 1, 2003

By G. Roy Chaudhury

Adsorption techniques are comparatively low cost and effective for treatment of arsenic contaminated drinking water. Various adsorbents such as alumina, ferrihydrite and manganese ores have been used, but there has been little investigation of modifying the structure of ferrihydrite to improve its adsorptive efficiency of As(III) and As(V). In the present study the incorporation of manganese oxide into the ferrihydrite structure was carried out and the prepared materials used in arsenic adsorption experiments. The compounds were X-ray amorphous, but TGA/DTA and FTIR analysis showed some structural characteristics. Sorption studies reported in this paper indicate the excellent arsenic removal properties of the manganese/iron compounds with a loading capacity of 0.3 mmol/g. Adsorption follows first order kinetics and the results fitted to adsorption and mass transfer models. Arsenic levels in water containing 1 mg/L As(V) were reduced by 50% in 20 minutes and 90% in 60 minutes using 1 g/L manganic ferric oxyhydroxide.

Jan 1, 2003

By Mitsuru Tanahashi

In order to develop an effective process for the production of a solar-grade silicon (SOG-Si) from metallurgical-grade one (MG-Si), the oxidation removal of boron from molten MG-Si was investigated at 1773 K by the following two CaO-saturated CaO-CaF2 flux treatment processes. I) Boron removal by flux addition onto the molten MG-Si followed by oxygen gas injection into the melt (Two-stage connecting process). II) II) Boron removal by simultaneous injection of flux powders and oxygen gas into the molten MG-Si (Simultaneous injection process). These processes can establish the special condition of both high basicity of the flux and the high oxygen partial pressure at the boron removal reaction sites. Through these processes, especially by the simultaneous injection process using a flux powder injection equipment, the boron content in MG-Si can be efficiently reduced. The obtained results clarified that both processes should be conducted for a time period as short as possible by using as much flux as possible. By repeating the simultaneous injection process for 60 s three times under the optimum operating conditions determined in the present study, the boron content in MG-Si can be reduced from 14 to 4.7 mass ppm.

Jan 1, 2003

By V. G. Papangelakis

The implementation of a flow-through yttria-stabilized zirconia (YSZ) sensor for pH measurements in high temperature and concentrated electrolyte systems relevant to hydrometallurgical processing of nickeliferous laterites is discussed. Instrumentation involved the use of a custom made flow-through titanium electrochemical cell. Accuracy and validity of the pH measurements at temperatures up to 250C were assessed using concentrated sulphate process solutions ranging from synthetic binary sulphuric acid ? water solutions to progressively multicomponent metal ? sulphate solutions simulating laterite Pressure Acid Leach conditions. The measurements were also compared with theoretical models using recently obtained thermodynamic data. A difference of ±0.25 pH units was observed between measured and calculated pH values at temperatures. This is an acceptable difference given that these are the first direct high temperature pH measurements ever on the concentrated acidic sulphate solutions. This result is encouraging more research for the development of industrial electrochemical systems for direct pH measurements in autoclaves.

Jan 1, 2003

By Huaming Yang

Infrared materials are a special kind of material widely used in military, biological engineering and chemical industry. However, the problems associated with them such as unstable properties, high cost and a high thermal expansion coefficient seriously restrict the development and the wide application of the traditional infrared materials with the SiC or ZrSiO4 matrix. The ultrafine quartz powder is normally used to prepare the infrared materials by hot-pressing technology. The aim of the paper is to investigate the thermal expansivity, the effect of the SiO2 size and the addition of AI2O) or Fe2O3 on the infrared emissivity of the quartz matrix of the infrared material (QMIM) in a 8-25um wavelength range. The results indicate that 89% of infrared emissivity and 0.4x 10.5°C of thermal expansion coefficient of QMIM can be obtained. The affeeting mechanism of Al2O) and Fe2O3 on the infrared emissivity of QMIM were also discussed.

Jan 1, 2003

By Takashi Araki

In this work, we have elucidated the two-step oxidative reaction mechanism of 2,4,5-trichlorophenol by adsorbing oxygen atom for oxidative decomposition reaction of 2,4,5-trichlorophenol on oxide catalyst surface using ab initio molecular orbital calculation. In the first oxidation, total energies of reaction products have been shown extremely stabilized at all oxidation positions. This reaction occurs due to charge transfer from benzene ring to adsorbing oxygen atom. As a result, ? bonding of benzene ring are weakened. However, the benzene ring of 2,4,5-trichlorophenol does not perform cleavage reaction. In the second oxidation, the benzene ring of 2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By Yoichi Takeda

The CaO-FeO,-Cu20 slag has been practically applied to continuous converting of copper, and also has potential for refining of copper. Liquidus lines of the slag system and phase stability diagram for the liquid slag and the existing solid compounds under copper saturation are presented. Liquidus composition was determined by chemical analysis of slag sample saturated primary solid. The temperatures of invariant equilibria were investigated by thermal analyses. Oxygen potentials on the liquidus lines, the univariant and invariant equilibria were estimated from the relation slag composition and oxygen potential that relation was confirmed in separate experiments.

Jan 1, 2003

By Sandra M. Stash

An integrated copper production complex includes mining, milling and smelting facilities which are usually at or near a common site, and sized to complement one another in capacity. There may also be an electrolytic retlnery serving the complex, but not always totally dedicated to its production. Mines and mills without co-owned smelters are not usually considered integrated. The first marketable product of an integrated complex is blister, or in some cases electrolytically refined copper. The nature of integrated operation brings together all of the environmental issues associated with copper production, but currently operating and newly planned facilities are required to anticipate these issues and meet stringent regulations. Older complexes, however, may have legacies of 50 or more years of operation unencumbered by current levels of environmental strictures: nevertheless, they must be remediated. Using examples from closure and remediation of the mining and mineral processing facilities in the Upper Clark Fork River Basin of Montana, the authors review some of the problems encountered since CERCLA&apos;s1 enactment in 1980, and the solutions to those problems, bearing in mind that not all of the problems and solutions were technical. Much has been written about the mines of Butte -the "Richest Hill on Earth" as it was known in its day and the mills, smelters and refineries they spawned. These facilities comprised an archetype of the integrated copper complex: from ore to metal in facilities serving and depending on one another. Many great stories of technological innovations and business triumphs have been told about Butte and Anaconda&apos;s mining history and the place The Anaconda Company occupies in that history. However, relatively little has been written about the final days: 25 years during which the once-great complex was closed, and the remnants of past glories were remediated after nearly a century of operation. This paper offers some insights from the real world affecting similar complexes still operating, and, hopefully, lessons for others just starting down the path to final closure.

Jan 1, 2003

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f&apos;), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003