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By J. J. Talja

An investigation of oxidation of various nickel concentrates was carried out using differential scanning calorimetry (DSC). The aim of this study was to determine the ignition temperature and investigate other oxidation behavior of various sulfide-based nickel concentrates. Variables in the experiments were mineralogy, particle size and partial pressure of oxygen with temperature increasing linearly at 25 K/min from 323 to 1023 K (50-750 °C). The igni¬tion temperature was determined to represent the starting point of rapid oxidation. The reac¬tion enthalpies of the concentrates were determined and the amount of heat generated up to various time were used to calculate the extent of reaction. Mineralogical changes at various stages of oxidation were also investigated. For this purpose a second set of DSC-experiments were carried out in which each experiment was interrupted at a desired temperature between 673-873 K. From these tests the weight loss of samples were determined and changes in the individual constituent of sulfide minerals were analyzed. For pentlandite-based Ni-concentrates the ignition temperature was 705-710 K (approximately 435 °C). Pyrite was the first sulfide to oxidize. Reactivity of the violarite-based concentrate was greater than those of the pentlandite-based concentrates. The stoi-chiometry of pentlandite changed before ignition because of preferential oxidation of iron. Rapid oxidation of the pentlandite mineral occurred at about 823 K (550 °C). By 900 K about 90 % of the iron in pentlandite was converted to hematite, and NiS containing some iron was formed.

Jan 1, 1994

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, 1£ 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 of2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By Juan Patricio Ibáñez

Separation of arsenic and copper from Cu-As-H2S04 electrolytes by electrodialysis has been investigated at room temperature. The effects of current density and pH were studied. An arsenic-free copper solution was obtained for all the tested conditions. The transport efficiency for copper ions was found to be higher than 98% after 3 hours' test. Transport of arsenic and copper through the ion exchange membranes was increased by increasing pH and current density. Solution pH was found to be a key parameter for the separation process, since it controls the speciation of the ions to be transported and the formation of unwanted precipitates which reduce the global efficiency of the electrodialysis process. The main conclusion is that electrodialysis is a promising technique to be used in separating and/or concentrating ions of interest in copper electrometallurgy.

Jan 1, 2003

By F. Begazo

The most common approach to increase production in copper refineries is to increase current densities. However, if these increases are not well thought out beforehand and are not properly and effectively controlled, the end results could be reduced plant performance and a deterioration in cathode quality. Both of these factors result in lower efficiencies and increased costs. At the Ilo Refinery of Southern Peru Copper Corporation, a modernization and expansion program was implemented shortly after the Refinery was purchased from Minero Peru, in 1994. This program was intended to increase production from 195,200 mtpy of cathode to 227,000 mtpy over a 3-year period. Part of this production increase would come from increasing current density. During the period from 1994 to 1997, current density at the Ilo Refinery was increased from 218 A/m2 to 230 A/m2, while plant efficiencies were maintained at consistently high levels. The current efficiencies were maintained at >97.5% and time efficiencies were maintained at >98%. During 1998, additional increases in current density were implemented while the high plant performance was maintained at the same levels. By the end of 1998, the current density was 241 A/m2, while current efficiency and time efficiency of 98% were maintained. This paper describes the control processes used at the Ilo Refinery to maintain high plant performance levels while increasing the current density. Additionally, expected plant performances from extended test programs at current densities up to 280 A/m2, for future production increases, are reviewed and discussed.

Jan 1, 1999

By Beate Ina Jenssen

Ferric iron removal from the nickel electrolyte at Glencore Nikkelverk AS in Kristiansand, Norway, is achieved by precipitation of iron hydroxide followed by filtration, and it is desirable to improve filtration properties of the precipitated iron hydroxide in order to decrease the filtration time. The effect of increasing the residence time from the current 45 min to 75 min and temperature from 65 °C to 90 °C on the filtration properties of the precipitated iron hydroxide (akaganéite) was studied by simulating the industrial process conditions in a continuous reactor setup operating at steady state, using ferrous-containing process solution as feed material. It was possible to decrease the filter cake resistance by both increasing residence time and temperature, but temperature gave the most pronounced effect and reduced the filter cake resistance by one order of magnitude.

By Dr. -Ing. Wolfgang Pietsch

Many primary metallurgical wastes are in the sh.-ape of turnings; borings, chips, dusts, and other particuletes. While such. materials can be easily segregated and/or upgraded to yield high quality ?secondary metals with often known composition for easy recirculation into the production? process; their particulate nature results in various problems. Roller presses are used in an ever increasing number for size enlargement and densification of primary particulate metallurgical wastes for secondary metal recycling. The paper will mention the areas of application from A(luminum) to Z(ink), also including Brass; Cast Iron, lead, and Stainless Steel, as well as dusts from all types of melting and ladle furnaces or converters. Typical systems using roller presses for size enlargement. will be discussed.

Jan 1, 1995

By Marcio B. Fonseca

Nickel-cobalt laterite deposits have become the focus of attention for hydrometallurgical processing. Following the lessons of the second generation high pressure acid leach (HPAL) projects in Western Australia other Ni-Co laterite projects are now evaluating potential HPAL projects with a rigorous integrated approach that begins with geological modeling, resource estimation and metallurgical studies. The Vermelho nickel-cobalt laterite deposit has been under exploration and study for several years with investigations of various metallurgical processes. Recent HPAL studies have indicated that the nickel and cobalt laterite at this deposit is amenable to upgrading by silica rejection followed by pressure leaching. These studies have required a detailed geological investigation to generate a new resource model. The recent development of a sophisticated geological model integrated with a multi-element resource estimation for this complex tropical nickel laterite deposit in northern Brazil provides an example of the contribution of geology at the critical project stage where process technology decisions are made on relatively small samples of the total resource.\ Keywords: Ni Laterite, Geological Modeling, Resource Estimation

Jan 1, 2004

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 Gui-fang ZHANG, Zhe SHI, Lei GAO

Secondary V-recycling slag, an industrial waste containing high gallium is being dumped continuously, which causes the loss of gallium. Thus, the alkali fusion process was employed to recover gallium from this slag. The effects factors on extraction of gallium such as roasting temperature, roasting time, alkali fusion agent concentration and CaO concentration were investigated in the paper. The experimental results indicated that excessive roasting temperature and roasting time is unfavorable to the recovery rate of gallium. The appropriate roasting temperature and duration are 1000 and 2 hours, respectively; The appropriate proportioning of Na2CO3: NaOH is 2:1 when the concentration of alkali fusion agent weighs 0.4 times the mass of the slag; In order to remove SiO2 from the leaching liquor, CaO should be used as an additive in the roasting process. The appropriate concentration of CaO should weigh 0.2 times the mass of the slag. Employing these optimal alkali fusion conditions in the roasting process, gallium recovery is above 90%

Jan 1, 2015

By M. J. Adam

The U.S. Bureau of Mines is investigating the partitioning of selected complex minerals into simple phases using sulfidation reactions. Successful partitioning of complex mineralogy to simple phases may afford an opportunity to improve selective extraction of mineral constituents of economic value. The research has shown that complex minerals, such as chalcopyrite (CuFeS2) and pentlandite [(Fe,Ni)9Se]' may be partitioned to the simpler phases covellite (CuS) plus pyrite (FeS2) and vaesite (NiS2) plus pyrite (FeS2), respectively. Demonstrations of these reactions were verified through long-react ion-time (24 h or more) experiments, but basic rate investigations and modeling were not included in the previous research. This report describes research aimed at determining the rate at which the complex mineral CuFeS2 converts to the simple sulfides CuS plus FeS2. Small samples of CuFeS2 were blended with elemental S prior to thermal treating under an He atmosphere for time periods up to 4 h. Products from each treatment period were characterized using metallography, chemical analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Results of the investigation revealed a rapid conversion of CuFeS2 to CuS plus FeS2 early in thermal treatment periods. As the reaction occurred, a CuS rimming of particles was observed which separated the reacting species (CuFeS2 and S) and caused a considerable decrease in transformation rate.

Jan 1, 1991

By Dirk Verhulst, V. I. Lakshmanan

Why Chloride Hydrometallurgy?The most available, cheapest and best known reagent for treating ores and other raw materials for the metallurgical industry is sulfuric acid. Hydrochloric acid is second in line. What often happens is that a process is developed on the basis of sulfuric acid, and that at some point the question arises: wouldn't hydrochloric acid do this better?Considering hydrochloric acid immediately opens a very interesting field of research. To summarize a few comments from another paper presented at this symposium [1]: chlorides are far more soluble than sulfates (with a few interesting exceptions); the hydrogen ion activity is greater in chloride than in comparable sulfate solutions; higher oxidative conditions are possible; regeneration is more straightforward; more diversity is possible and better conditions for the separation of species can be found for solvent extraction and ion exchange; sulfur in the ore can be separated as elemental S; higher metal concentrations in solution and more flexibility in the chosen oxidation state means significantly lower energy costs.Also, the volatility of many chlorides at higher temperature allows further separation without the need to go to a different system. Chlorides also form molten salts with a low melting point, providing another means of separation and purification in the same chloride medium.

Jan 1, 2011

By Sheng-hai Yang

The ultrafine, monodispersed, spherical cobalt powder has been fabricated by reducing cobalt hydroxide with glycol. It were investigated that the effect of NaOH concentration on the reaction rate and the effects of the concentration of cobalt hydroxide and surfactant on the morphology and particle size. The particles were characterized by the X-ray diffraction(XRD), scanning electron microscope(SEM), laser diffraction particle size analyzer and BET specific surface analyzer respectively. The XRD shows that the cobalt powders exist mostly in face centered cubic (fcc) structure, a little in simple hexagonal. The cobalt powders prepared at Co(OH)2150g/L, NaOH 40 g/L and surfactant 30g/L, its average particle size, specific surface area and cobalt content, were 0.88µm, 2.705m2/g. and more than 99.5% respectively.

Jan 1, 2006

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reproducible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CU2S-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in Cu2S-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at I200°C; (iii) Phase equilibria and thermodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thermodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By F. Kassabji

This publication presents the main experimental and theoretical results on the recovery of aluminum scrap (dross and Used Beverage Can) without use of any addition of fluxing salts. Dross and UBC's processing experiments have been conducted in a rotary plasma furnace operating in the transferred and non-transferred mode, using different plasma gases. The investigation involved the treatment of more than 100 kg of dross and other aluminum residues using plasma torches with less than 100 kW power. The experimental work showed that this process is .far more economical and kind to the environment than the conventional route using a salt flux. An equilibrium thermodynamic calculation at elevated temperature makes possible the prediction of by-products at various temperatures for different plasma gases.

Jan 1, 1994

By Nagahiro Saito, Takahiro Ishizaki, Mituhito Hirota, Akio Fuwa

"Owing to their extremely high toxicity in the environment, the dioxins have been attracting social, technical and scientific attention in recent years. The authors theoretically had predicted the thermodynamic properties of all the dioxins via quantum chemistry and statistical thermodynamics and elucidated the generation-decomposition behavior of dioxins in the equilibrium calculation· of C-H-0-Cl system. In actual combustion processes, it is said that metallic compounds have much influences on the dioxins behavior. The aim of this study is to reveal the roles of metallic compounds the generation-decomposition behavior of dioxins is revealed from the viewpoints of quantum chemistry. Especially, the catalytic effect of copper has been investigated for the reaction, 2HCl(g)--H2(g}+Cl2(g) and for the etherification reaction from precursors, which is Phenol(g) here, to dioxins. The catalytic role of Cu is shown to have much influence on the generation -decomposition of dioxins.1. IntroductionIt is well known that dioxins are very harmful not only for our health but also for that of our children and grandchildren because they are very stable substance and their reaction rates of decomposition are considerably low. On the other hands, it is not well know how dioxins are generated and decomposed; the generation-decomposition conditions and paths as well as the catalysts to decompose them'1l. The authors believe that the thermodynamic and kinetic study of dioxins is useful to find a solution to these issuers. The authors have been investigating the following problems to reveal the generation-decomposition behavior of dioxins; (a) the prediction of the thermodynamic parameters of dioxins (2), (3), (b) the generation -decomposition behavior of non-chlorinated dioxins by the thermodynamic equilibrium calculations in C-H-O system(4) and (c) the generation-decomposition behavior of dioxins by the thermodynamic equilibrium calculations in C-H-O-CI system(5). Summaries of these thermodynamic researches are as follows.(I) The thermodynamic parameters for dioxins, which had been unknown and/or inaccurate'6 l, could be predicted and are available within the scientific accuracy."

Jan 1, 2000

By John G. Reid

When the paper "Operations at the Greenvale Nickel Project Mine and Refinery" was delivered at the 1st International Laterite Symposium in February 1979, the Yabulu Caron plant had been operating for four years and production had just stabilized. The design had been based closely on the Caron plant at Nicaro, Cuba, built in 1944, also by Freeport. Yabulu had 10 Herreshoff ore roasters and production in 1978 was 18,682 tonne nickel as impure oxide sinter and 763 tonne cobalt in a mixed sulphide with a cobalt to nickel ratio of 1 :2.5. In the 25 years since the 1st Symposium, two more roasters have been added, but dry ore processing rate has remained relatively unchanged at 2.4M Uyr to allow a lower feed rate per roaster with associated higher recovery. The ore source has changed from the domestic Greenvale mine to imports from New Caledonia, Indonesia and the Philippines. Nickel production between 1978 and 2003 has risen by 67%, cobalt has risen by 146% and the products have changed to high purity nickel compacts and "ChemGrade" cobalt salt. The plant changes that have contributed to the increased recovery, production and product value are discussed. Keywords: Caron, Yabulu, nickel, cobalt, ammonia

Jan 1, 2004

By R. Harris

Blister copper melts of 800 g to 1000 g containing less than 1 wt % S and up to 3 wt % Ni were desulfurized at 1523 K in air or by a pure oxygen jet blown at 75,500 and 1000 cm3/min, from 1 cm above the melt. Rates of desulfurization and oxygen pickup were measured and visible surface phenomena were photographed and videotaped. It was observed that SO2 was evolved from Cu-S melts in a manner reminiscent of the effervescence seen in carbonated drinks. The effervescence lasted up to 20 minutes and resulted in the ejection of material up to a height 50 cm above the melt surface. Sporadic discharge of large bubbles was also observed in a Ni containing melt top-blown with oxygen at 1000 cm3/min. The Cu-S melts top-blown with oxygen experienced faster sulfur elimination as compared to stagnant melts exposed to air and experienced only a single period of turbulent SO2 evolution, which occurred almost immediately after oxygen injection commenced. The Cu-S melts exposed to air experienced multiple episodes of effervescence. The stagnant blister copper melt containing nickel did not exhibit effervescent behaviour and experienced a lower rate of sulfur elimination compared to Cu-S melts tested under similar conditions. The present article examines the role of surface phenomena in determining the observed behaviour.

Jan 1, 1999

By LuisW. Pommier

The industrial wastes generated by the plating industry, the circuit board manufacturing industries and other related industries normally contain high concentrations of metals, which make them hazardous. The extraction of the contained metals and their separation may be achieved by both pyro and hydro metallurgical processes. Some of the industrial wastes, those rich in some metals like nickel for instance, are being treated like mine ore concentrates and are being fed to smelting furnaces. The slags from these smelter operations are hazardous. They have, however, special environmental dispensations issued by the regulatory authorities. Hydro-metallurflcal processes have been reported. They also generate a residue which is hazardous because not all the valuable metals are leached out and also, because "non valuable" components, like chromium, are less readily leached. Residues from the plating industry, containing nickel, copper. zinc, iron and chromium as the major constituents and also sodium and calcium, together with cadmium, cobalt, lead. manganese, magnesium, molybdenum, and potassium, have been processed for the extraction of the valuable components. The generation of electrolytic nickel, copper and zinc and also of ferric chloride and chromium oxide is reported. The operation is achieved by a caustic leach for the extraction of zinc, followed by a sulfuric acid leach for the extraction of nickel and copper. This acid leach also extracts the iron and some chromium. The nickel copper and zinc are rendered pure by electrolysis, the iron is oxidized for the production of ferric chloride and the chromium is recovered as an oxide. The leaching operation is performed in two stages, first at a pH of 2.5 to generate an electrolyte for the partial recovery of the metals and then at a pH of 0.5 for the complete extraction of the metals. This leaching operation generates a residue, which although small in volume compared to the initial feed, still contains traces of the valuable metals and a portion of the chromium which makes it hazardous. Additional leaching with hydrochloric acid or nitric acid is required for its complete dissolution. The other minor constituents mentioned are present in concentrations each of less than 0.1% and are handled as impurities in the process. The metals which are soluble at a pH 0.5 and precipitate between 0.5 and 2.0 are bled off. Other impurities will concentrate on the raffinate from the solvent extraction operations from whence they are bled off. These bleeding streams are hazardous and the "impurity metals" are now present in concentrations which would make them valuable, however, the size of these streams is so small that they do not warrant their processing, however they could be marketed to specialized smelters. The extraction of the valuable metals, of the hazardous constituents, the generation of a marketable mixture of minor constituents and the production of a non-hazardous residue for declassification is profitably achieved.

Jan 1, 1998

By Andreas Orth

Outokumpu Lurgi Metallurgie has developed a process for the calcination and reduction of laterite nickel ore tines where the reduction of iron and nickel to the wustite/metallic states respectively, is performed in a fluidized bed reactor using reduction gas generated very cost effectively from natural gas in an autothermal catalytic reactor. As an option coal can be used as reductant as well as additional fuel. The process of reduction and calcination is very energy optimized. It uses the off gas from the fluidized bed reduction reactor, which still contains energy, to dry and calcine the nickel ore fines in a primary stage circulating fluidized bed (CFB) reactor. The product shows high metallisation of nickel and iron oxides reduced to the wustite stage. This results in considerable energy savings in smelting the prereduced product to ferro-nickel. Alternatively the product can be leached to produce nickel. Laboratory tests showed very high recovery of nickel and cobalt. Keywords: Fluidized Bed, Prereduction, Calcination, Ferro-Nickel

Jan 1, 2004

By S. Abe

Various copper anodes to be electrorefined were subjected to a heat treatment comprising annealing at a temperature in the range of 700 °c to 1,000 °c followed by a slow cooling preferably on the order of about 150 °c, and using these heat treated anodes , a series of dissolution experiments were conducted under conventional electrorefining conditions. The results obtained have indicated that the above annealing/slow cooling process dramatically improves the dissolution activity regardless of the type of anodes. As an example, passivation times of l to 3 minutes in a standard test have been increased to more than 80 minutes by this innovated heat treatment. Other advantages sterning from the improved anodic activity include reduced electrical short circuiting which results in substantial labor effort in the tankhouse, reduced energy requirement, and reduced cost of processing anode slimes because the amount of anode slimes is reduced. In addition, this process gives rise to a dramatic change in the nature of anode slime layer formed in such a way that a comparable final cathode copper product can be achieved even from high-impurity copper starting material.

Jan 1, 1987