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By Takafumi Kondo, Satoshi Yamashita, Noboru Masuko

"Aqueous oxidation of phosphite ions to phosphate ions with dissolved oxygen was examined at 80° C and pH 4.5 mainly from the stichiometric point of view. Dissolved oxygen alone can not oxidize sodilim phosphite in aqueous solution, but when sulfur dioxide is coexistent, cooperative oxidation for both sulfite and phosphite can occur in aqueous solution. Sulfur dioxide itself is well known as a reducing agent, but it also reacts as an oxidation-promoting agent for other species under a certain condition. So sulfur dioxide is· a promising cheap reagent for waste phosphite processing.IntroductionIn a liquid-phase oxidation reaction using the dissolved oxygen gas, the eoexistence of a copper salt is required generally. Recently, it was reported that the oxidation reaction progressed by using mixed gas of sulfur dioxide and oxygen without the copper catalysis, and the attention has been collected1·3). The present authors also noticed the phenomenon since the early time and have been studying on the reaction mechanism of sulfur dioxide in liquid phase oxidation 4l. It was found that; by using the SO2-O2 mixed gas, the oxidation of phosphite ions to phosphate ions proceeded efficiently in sulfuric acid solutions. In the present report, the applicability of SO2-O2 mixed gas as a cheap oxidizing agent to the industrial processing of the waste solution of electroless nickel· plating is investigated. It is well known that the sulfur oxide dissolved in aqueous solution is oxidized ·by the oxygen in the air to sulfuric acid according to the following equation"

Jan 1, 2000

By Edgar Peek

Lixiviant regeneration is by definition a precondition for any hydrometallurgical process. In chloride hydrometallurgy either HCl or Cl2 has to be regenerated in order to establish an economically viable metallurgical process. One such regeneration process is widely used with steel pickling where HC1 is regenerated through the thermal decomposition of ferrous chloride in either spray roasters or fluid bed pyrohydrolyzers. This standard HC1 regeneration process deserves to be considered as a potential separation process, since thermodynamic calculations show that a fluid bed pyrohydrolyzer can function as a ferrous-nonferrous separator. Several nonferrous,metals such as zinc, lead and cadmium can be volatilized as a chloride under ferrous chloride pyrohydrolysis conditions. If such a nonferrous metal volatilization could be achieved in the case of slurry feeding of "contaminated" iron oxides, then this would increase the Fe/H2O ratio of the (process) feed and thus save on fuel per ton of iron, while yielding a marketable iron oxide product. Previous test work on synthetic materials revealed that the near-complete separation of zinc, lead and cadmium from iron oxide was possible in a pyrohydrolytic atmosphere, even if zinc was present as zinc ferrite (more than 99.5%). This investigation, which was carried out in a tube furnace at 1100 K has now been extended to treat synthetic zinc minerals and also franklinite ore. For the latter, it was found that 85% zinc volatilization could be achieved in 4 hours at 1300 K. It is postulated that complete zinc volatilization could not be attained due to the formation and/or presence of gahnite and hardystonite, which might be stable in HCl/H2O atmospheres at 1100 K. The effect of adding small amounts of calcium chloride to react with gahnite and hardystonite to give zinc chloride and both calcium aluminates and silicates is being discussed. Test work on slurry feeding of this complex ore in a recently constructed 4-inch diameter fluid bed pilot unit has been planned for the near future.

Jan 1, 1995

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By Gaifeng Xue, Lei Zhang, Xia Liu, Lina Wang, Pu Liu, Benquan Fu

"Experiments were conducted to investigate the behavior of the integrated process with a three-dimensional electrode reactor combined with Fenton process for coking wastewater treatment. Effects of initial pH value, reaction time, H20 2 dosage, Fe2+ dosage on Total organic carbon (f OC) removal rate were investigated. The kinetics of degradation of TOC from coking wastewater by three-dimensional fluid bed electrode reactor combined with Fenton process was also studied. Experimental results shows that three-dimensional fluid bed electrode reactor combined with Fenton process had better synergic effect, average 17.4% TOC removal rate was improved within an hour. It was found that TOC degradation in coking wastewater followed a pseudo-first-order reaction kinetic model. The optimum degradation efficiencies of TOC were up to 60% as pH3.4, 3.5 mM ofFe2+ andl.2-1.8ml/L H20 2 in 90min reaction period. Furthermore, the integrated process showed a rapid reaction performance at a low temperature within a short reaction time and remained high efficiencies for TOC removal. Overall, the integrated process was proved feasible for coking wastewater treatment in practical applications.IntroductionCoking wastewater is generated from coal coking, coal gas purification, and by-product recovery processes of coking, which is composed of phenolic compounds, heterocyclic compounds, polycyclic aromatic hydrocarbons, ammonia, cyanide, polycyclic nitrogen-containing aromatics, acyclic compounds, etc. Most of these constituents are refractory, poor biodegradability, toxic and carcinogenic['-31. Currently, coking wastewater is usually treated by different forms of A/O biological nitrogen removal process as the primary treatment process, but the aforementioned processes are not efficient enough to meet the requirements from the National Discharge Standard in China (GB13456-1992). According to the continuous requirement on improving environmental protection for coking industry (revised 2008), increasing wastewater utilization ratio and reducing discharge of effluent in the coke industry has to be implemented for cleaner production and sustainable development. Therefore, advanced technologies need to be developed to treat coking wastewater and reutilize the product as industrial cooling water, which would be one of the best choices to achieve zero discharge of wastewater and reduce water consumption per ton of steel [4-51 . In this study, three-dimensional fluidized bed electrode reactor combined with Fenton process was adopted to advanced treatment of coking wastewater, and the effects of operating conditions, including H2O 2 dosage, Fe2+ dosage, initial pH, and reaction time on TOC removal rate, were investigated. Meantime, study of kinetics of reaction was estimated."

Jan 1, 2013

By Lv Guozhi, Ren Xiaodong, Liu Yan, Dou Zhihe

"This paper investigated a new desulfurizer, dolomite and ferrosilicon. Magnesium vapor produced by silicothermic reduction of dolomite and ferrosilicon in an immersion tube of molten iron was injected into the molten iron by carrier gas through the underpunch of the tube and desulfurization reaction occurred. In order to explore the desulfurization process of molten iron by the new desulfurizer, the thermodynamics, and experiments of magnesium vapor production and desulfurization have been studied. Through thermodynamic calculation, the reaction temperature of magnesium vapor production by 75ferrosilicon and light-burned dolomite is 1838K in the standard state and decreased with the decreasing partial pressure of magnesium vapor, PMg· When PMg=25kPa, the reaction happens at 1673K. From experiments of magnesium vapor production, reduction efficiency of Mg vapor is about 60 % in 15 minutes at 1673K. From hot metal experiments, the desulfurization efficiency is 89.35%, and the lowest sulfur concentration after desulfurization is 46ppm.IntroductionPretreatment desulfurization of hot metal has become a necessary step in modem optimizing steelmaking process for its cheap cost, which can not only liberate of blast furnace productivity and reduce the burden of produce steel, but also effectively improve overall economic efficiency of the iron and steel system[l-ZJ_ At present, injection magnesium particle is one of the two main methods of desulphurization in hot metal owing to its strong affinity for sulphur, low amount of slag produced, low iron loss in slag skimming and low equipment investment[3l. However, there are still some insufficiencies on the hot iron pretreatment with magnesium particles at present[4-5l"

Jan 1, 2013

By L. Cifuentes

Electrodialysis (ED), i.e. a technique based on the effects of electrically charged membranes on ions in solution in an electric field, has been applied to Cu-Fe-As-Sb- H2SO4 electrolytes similar to those used in copper electrorefining and electrowinning operations. The effects of current density, time and species concentration have been studied in a batch ED cell. The technique has shown to be effective in concentrating and separating a range of ions and points to possible new methods of treating copper electrometallurgy effluents.

Jan 1, 1999

By J. F. Elliott

The thermodynamic behavior of sulfur and oxygen in copper matte has been measured by equilibration of the melt 00 a gas consisting of CO, SO2 and Ar. The oxygen potential ranges from 10-9 to 10-7 and that for sulfur from 10-4 to 10-2 atm. The work is a continuation of the earlier study by Luraschi and Elliott in our laboratory. A model has been developed that permits extra-polation of the results to ascertain compositions of the matte that are saturated with various oxides of iron.

Jan 1, 1983

By M. Kobayashi, Y. Nishisu

"Fine multicomponent particles of yttrium and europium were synthesized through the precipitation from homogeneous solution, and the various characteristics related with the fluorescence were investigated. The morphology and the fluorescent characteristics of the synthesized particles were affected by ionic species in the stock solution. In the presence of sulfate ion, some parts of the precipitated particles were aggregated, and _the fluorescent characteristics were not good. On the other hand, in the presence of chloride ion or nitrate ion, the particles precipitated were almost monodispersed, and, the intensity of the fluorescent emission were strong after calcination. Further, these particles were also very attractive as the red phosphor in the mercury-free fluorescent systems.Introduction Eu doped Y oxide particles have been widely investigated for the application to the fluorescent lamps and displays: Recently, the fluorescent lamps are pointed as harmful electric equipments because of using mercury for excitation. Therefore, the use of the mercury in the fluorescent- system will be limited or prohibited worldwide in near future. Then, the development of the mercury-free fluorescent lamp is strongly required without delay. Inert gas such as neon and/or xenon seem to be applicable as new excitation element that replaces the mercury. However, in case xenon the excitation wavelength,' 146 and 172nm, is different from that of the mercury, 254nm, and then, the commercial phosphors which are used in the present fluorescent lamp system are not available. Therefore, the invention of the novel phosphors is essential for the development of the mercury-free fluorescent lamp. Further, the controls of the size and shape of the particles precipitated are also important, because the homogeneity of the size and the shape is very important for the fabrication of the layer of the phosphor particles. That is to say, the development of the phosphor particles with controlled components, size and shape is essential. The precise control of size and shape improves the packing density, and so, the screen performance of the lamp [1]. In addition, these phosphor particles should be also useful for the application of the flat-plane displays, for example, PDP, etc. [2,3]. In the present work, first, the particles including yttrium and europium for the precursor for red phosphor were prepared through precipitation from homogeneous solution. This process was precisely controlled for the control of the components, size and shape of the particles precipitated. Next, the particles precipitated were calcined, and then, their fluorescent properties were characterized. As a result, some of them showed the possibly available characteristics as the red phosphor for mercury-free fluorescent lamp system. These experimental results are presented in this paper."

Jan 1, 2000

By A. N. Lasseigne

Hydrogenation behavior of the NaAlH4 intermetallics is investigated utilizing thermoelectric power and magnetic analyses. Using both thermoelectric power and magnetic susceptibility measurements on these intermetallics allows for confirmation and further insight into hydrogen's role in altering the material's electronic structure. The electronic and magnetic property correlations will indicate the direction for further alloy development to optimize hydrogen storage.

Jan 1, 2006

By H. Kandemir

An experimental study of the bacterial oxidation of naturally occurring high-purity sulphide minerals (FeS2, Fe1-xS, Cu5FeS4, ZnS) is presented using a mesophilic strain of T. ferrooxidans. As well as metal analyses and solution pH, partitioning of sulphide sulphur into elemental sulphur and sulphate has been monitored as a function of leach time. Partially oxidized sulphide substrates have been characterized, at regular time intervals, by X-ray diffraction methods and extracellular organic compounds reporting into leach solution .have been identified by thin layer -chromatography.

Jan 1, 1985

By Cheng Fang, Zhou Lie-xing, Peng Jin-hui, Guo Sheng-hui

This article discusses the behavior of temperature and microwave thermo gravimetric analysis characteristic of ammonium paratungstate in a microwave field. Experimental results show that when 12g of material is place in a microwave with 900W of power, paratungstate’s temperature rises at 70°C/min. This results in paratungstate’s temperature being 980°C after 14 minutes. Compared with thermo gravimetric analysis characteristic, former two-step process of paratungstate microwave calcined completed ahead of schedule, after two-step process reaction is more intense,Paratungstate warming is more rapidly, the reaction time is much shorter; According to XRD and SEM, the product is high purity, the crystal particle size is uniform, and the grain size is fine.

Jan 1, 2015

By Sanaz Mosadeghsedghi

The feasibility of the application of electrodialysis in separation of light and heavy rare earth elements (REE) in synthetic solutions was investigated. The experiments were carried out using single and binary solutions of a light (cerium) and heavy (ytterbium) REE. The effects of electrical voltage, electrical current, and the addition of complexing agent (EDTA) to increase the separation selectivity were investigated. Separation of Ce and Yb was achieved in binary solutions with and without the addition of EDTA. Higher degrees of separation were seen at higher voltages. Ce–Yb separation was more significant in the presence of EDTA. The separation factor of Ce–Yb and Ce–Yb-EDTA were 1.44 and 2.60, respectively.

By Dinesh P. Amalnerkar, Nagegownivari Munirathnam, Tirthalli Prakash, Katia Vutova, Vania Vassileva, Veliko Donchev

"A time-dependent model for electron beam melting and refining (EBMR) of different metals and alloys is developed. The model is 3D axi-symmetrical and an adapted numerical scheme of Pismen-Rekftord type is applied. The developed computer program computes the thermal fields in the metal ingots during EBMR process as well as the dynamics of the thermal streams and the geometry of the molten metal pools. Calculated results for different regimes of EBMR of titanium are obtained and discussed in the paper. Experiments are performed and impurities' concentration data are presented. Simulation results are compared with experimental data and are used for optimization of the EBMR process in the case of Ti.IntroductionElectron beam melting and refining (EBMR) has an important role in the special electrometallurgy[ 1-6] and it is approved for obtaining of pure titanium [7]. EBMR of metals and alloys is being recognized as a competitive and even the single method for obtaining new materials for all areas of human activity.The principal scheme of the EBMR drip process is shown in Fig.1. A thin layer of molten metal is formed on the front part of the feeding rod during the e-beam processing and generated droplets fall into the molten pool in the crucible where the ingot is formed. The refining is mainly realized at the boundary liquid metal - vacuum. There are three zones in EBMR (Fig.1) - on the front part of the feeding rod (zone I in Fig.1 ), on the surface of the generated droplets (zone II in Fig.1) and the surface of the molten pool in the water-cooled copper crucible (zone III in Fig.1)."

Jan 1, 2013

By Katerina Kryst

Antimony and bismuth are two of the elements that need to be removed from copper electrolyte to ensure a trouble free operation as well as to maintain copper cathode purity. One method to control these impurities is the use of aminophosphonic ion exchange resins. Antimony is present as both Sb(III) and Sb (V). Sb(V) is very difficult to remove from these resins, requiring excess amounts of highly concentrated hydrochloric acid. In industry this affinity of Sb(V) for the resin causes a buildup of Sb(V) and degrading resin performance due to continual reduction of resin capacity. A new method for regeneration of aminophosphonic resins loaded with Sb(V) has been developed, which utilizes catalytic regeneration of the resin. Ion exchange can then be utilized for continual control of Sb and Bi in copper electrolyte.

By Jay R. Hitchings

A technique that enables excellent color photograph production from black and white negatives of electron microprobe x-ray images is described in this paper. The photographs are made by superimposing one, two or three negatives of black and white x-ray images individually through assigned primary color filters directly onto color print paper. When used to examine metallurgical or geological microstructures, the resulting color photograph provides detailed, qualitative information about spatial arrangements, elemental associations and relative concentrations of at least three elements. The technique is simple and straightforward, requiring only standard darkroom equipment. The use of color to display or present complicated microprobe data also allows a non-technical reader or audience to better understand the data.

Jan 1, 1981

By Hannu Johto

Boliden Harjavalta has operated a flash smelter for nickel sulphide concentrates in Finland since late 1959. The original nickel flash smelting process was modified in 1995 to a novel nickel matte smelting (DON) with semi-low iron where the batchwise operated converting became obsolete. Since that, the process has been applied to multiple chemically variable nickel sulphide concentrates with high environmental performance. In this paper, the status of the current smelter operations is described together with the recent modernizations of the nickel flash smelting furnace and the slag cleaning furnaces.

By Rodney Hundermark, July Ndlovu, Lloyd Nelson, Phillimon Mukumbe, Paul van Manen, Whitey Seyanund, Bart Pieterse, Bertus de Villiers, Diale Mokwena

The 2003 redoubling in power to 68MW on the Polokwane Smelter furnace represented a significant intensification in platinum group metal (PGM) smelting. Combined with onerous ‘green’ PGM concentrate smelting requirements, this yielded conditions unusually corrosive to copper coolers and refractories. This presented unexpected operational and design challenges to reliable crucible operation and maintenance. Combined with specific operational control intervention, development of protective coatings has led to the life of water-cooled copper components improving from 9 to 40 months. The furnace matte endwall was extended in 2010 to address accelerated wear of refractories and the potential risk for contact of copper components by superheated matte. An 18 month planned endwall rebuild cycle has been demonstrated (versus catastrophic failure within 9 months). Finally, benefits including lower energy consumption, improved metal recoveries and higher productivity resulting from operational and in-house design developments will be described, that justify “Celebrating the Mega-scale” in PGM smelting.

Jan 1, 2014

By Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa

"Thermodynamic properties of impurities in molten silicon are of prime importance in developing economical production methods of solar grade silicon. In the present research work, thermodynamic properties of boron, the most difficult element to remove from molten silicon, were measured by chemical equilibration techniques at 1723 and 1773 K. Activity coefficients and self-interaction parameters of boron in molten silicon were determined by equilibrating the melt with solid BN under controlled nitrogen partial pressures. Interaction parameters between boron and nitrogen in molten silicon were also determined by equilibrating the molten Si-B alloys with solid Si3N4• Based on the data obtained, the stability diagram of the Si-B-N system was established.IntroductionPhotovoltaic power generation using a silicon solar cell is expected to be the most promising energy source, because it is inexhaustible, cleaner and more safety than conventional energy sources, such as thermal or atomic power generation. At present, expensive off-grade silicon for semiconductor (SEG-Si) is used for a solar cell production. However, if a large-scale photovoltaic energy conversion using silicon solar cell comes into wide use in the near future, silicon will be sure to be in short supply for the cell. Therefore, a development of a new large scale process for solar grade silicon (SOG-Si) production is definitely necessary, which can remove contained impurities from silicon.Among the impurities contained in silicon, boron is one of the most difficult ones to remove by a zone melting or an unidirectional solidification, because its segregation coefficient in silicon is close to unity (0.8). In addition, boron behaves as a p-type silicon semiconductor dopant and, therefore, its content in SOG-Si must be severely controlled. Although some attempts to remove boron by various metallurgical methods have been carried out [I -4], quantitative analysis has not been made due to lack in the information on the thermodynamic properties of boron in molten silicon. From this view point, the activity of boron in molten silicon was determined in the present study by chemical equilibration techniques at 1723 and 1773 K."

Jan 1, 1998

By Zhiqian Zhang, Chao Wu, Chao Li, Hongxu Li, Chuanqi Jiao

"Many used electronic and optical products contain cerium of rare earth oxides, but it is difficult to recover such rare earth compounds by traditional metallurgy methods. The proposed supercritical water metallurgy is a novel way, perhaps it will be very helpful for rare element recycling, but the thermodynamic properties at such special systems is not clear. In the paper the H20-CeO-CeO2 and H2O-CeO2-Ce2O3 ternary system phase diagram were produced under the pressure of30MPa with different temperature of350°C, 375°C and 400°C. The stability existing area of possible cerium compounds and different ions like Ce2+,Ce3+,Ce4+,W,HO2-,0ff ,CeOH2+,CeO+ and CeO2· were determined.IntroductionCerium is an extensively used metal element playing an important role in the rare earth elements. CeO2 is an apparently simple binary oxide with cubic fluorite structure [l]. Ce0O gives rise to a range of important technological applications because of its oxygen storage capacity at moderate temperatures as below: CeO2=CeO2.x+ X/2O2 [2]. The oxygen storage phenomenon gives ceria important technological uses in different fields as automobile exhaust purification catalyst [3-4], fluorescent powder, ultraviolet absorption material [5], polishing powder, fuel cell materials [ 6], and gas sensors, etc. The excellent properties of CeO2 nano powder make its synthesis and preparation become one of the hot spots of world scientists study."

Jan 1, 2013

By Katsuyoshi Tatenuma

"In order to mitigate the effect of global warming by preventing the accumulation of atmospheric CO2, a permanent fixation method of surplus CO2 as an insoluble mineral onto the sea bottom is proposed. As the proposed reduction method of atmospheric CO2, the concrete concept of this method is to form an insoluble carbonate mineral (CaCO3) by direct electrolysis of the seawater; Ca2++2HCO3 -+OH- ? ?CaCO3(insoluble)+CO3 2- (soluble)+H++H2O <not as coral reef reaction>, are directly disposed of itself onto the sea bottom. By this treatment, a concentration of carbonate is reduced in the section of superficial seawater, and therefore the absorption capacity of atmospheric CO2 increases depending upon the shift of chemical carbon equilibrium between the mass of superficial seawater and the atmosphere. As no additives are required, or no secondary waste are produced, the proposed method assuming as green-orientated, has possibility to resolve fundamentally the problem of global warming in a green orientate manner.IntroductionRecently, the amount of atmospheric CO2 has been exponentially increasing and it is a main greenhouse effect gas causing the global warming [1, 2]. The concentration of atmospheric CO2 has increased more than 30% (370ppm in 2001) during only last two centuries, therefore approximately 750 Gton-C of CO2 currently exist in the atmosphere, in which 180 Gton-C of CO2 are accounted for the increment during two centuries [1, 3, 4]. In order to avoid the progressive increase of CO2 global abundance, 3 Gton-C of the incrementing amount per year [4], have to be removed annually from the atmosphere."

Jan 1, 2008