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By Ryo Sasai, Takeshi Itakura, Haruki Imaizumi, Hideaki Itoh

"Emission of industrial wastewater containing harmful oxoanions is one of the serious problems on account of its toxicity and the environmental pollution, especially caused by boric, phosphinic, arsenic and antimonic species. In this study, we developed a novel treatment technique of such polluted-water by hydrothermal mineralization. The treatment is “Geomimetic” method for precipitating oxoanions in aqueous media as natural ore resources by using hydrothermal treatment with calcium salts mineralizer. The treatment made it possible not only to detoxify the polluted-water, but also to recover the calcium minerals such as Ca2B2O5·H2O, Ca5(AsO4)3(OH), etc. Concentration of each ion in treated-water was lower than that of effluent standard in Japan. Moreover, the residual concentration of each ion was independent of the initial concentration, but it depends only on the solubility of the formed mineral under hydrothermal condition. Therefore, the hydrothermal treatment could be recommended as one of the treatment techniques of polluted-water.IntroductionVarious oxoanions such as boron and arsenic oxo-anions have high toxicity against human health and the environment. They are important resources, however, for plating or advanced material manufacturing industries[1-3], from which the wastewater containing these oxoanions is generated every day. An appropriate treatment is often required for industrial wastewaters to attain national effluent standards of Japan (NESJ, B: 10 mg/dm3, As: 0.1 mg/dm3). On the other hand, there is no production of arsenic and boric resources in Japan, and they are expected to be recycled. Therefore, the establishment of a system for the removal and recycling of arsenic and boron from wastewaters is of global significance.Several methods to remove them from aqueous media have been already reported by using adsorption[4], electro-coagulation[5], membrane separation[6-8] and biological techniques[9]. However, these methods have the following problems because of their stability in water. (1) Removal yield is low, especially for tri-valent arsenite ion (AsIIIO3 3-) and borate ion. (2) The applicable concentration range is narrow. In addition, the used adsorbents or collected residues after treatments are sill hazardous wastes, so that they must be treated by a proper method. But, it is very difficult to convert them to recyclable resources at most industrial plants. These problems are caused by the difficulty to recover these oxoanions as stable solid precipitates with low solubility in water. The establishment of recycling system of these hazardous compounds will be one of the world-important issues, especially, in Japan, which is poor in natural resources. On the other hand, compounds that contain high arsenic concentrations and are insoluble in water, are often found in natural minerals, for example, as haidinglite (Ca(AsO3OH)·(H2O) or Johnbaumite (Ca5(AsO4)3(OH)). This fact suggests that nature has an ability to produce insoluble As-bearing minerals. Similar phenomena can be found in case of boron, antimony, etc."

Jan 1, 2008

By Olga Karabelchtchikova

Keywords: Multipass grinding, Residual stress, Retained austenite, X-ray diffraction The study investigated residual stresses behaviors and their superposition effect in D2 dies for thread-rolling applications. A nested factorial experiment was applied to test hypotheses that the residual stresses profiles change due to combination of heat treatment and multipass grinding operations, and that certain patterns can be derived due to the memory relationship between pre-existing and final residual stresses distributions. The amount of the retained austenite along with residual stresses in variation with depth was measured using x-ray diffraction technique. Statistical analyses indicate that the proposed hypotheses hold. Residual stresses distributions as well as tensile peak location were found to be significantly influenced by the treatment parameters used. Unique characteristic patterns in the residual stresses profiles were observed due to multipass grinding technique across all experimental conditions. This finding suggested a plausible memory relationship between the cutting passes, and the causes of the foregoing results are further proposed and discussed.

Jan 1, 2005

By Hirokazu Narita

Keywords: solvent extraction, precious metals, thiodiglycolamide, rapid separation, hydrochloric acid The solvent extraction of some precious metals (Pd(II), Pt(IV), Rh(III) and Au(III)) and base metals (Fe(III), Cu(II) and Zn(II)) in a hydrochloric acid solution was carried out using N,N'-dimethyl-N,N'-dioctyl-thiodiglycolamide (MOTDA) dissolved in the mixed solution of 80 vol-% dodecane and 20 vol-% 2-ethylhexanol. The extraction percentages of Pd(II) and Au(III) in the 0.01 M MOTDA-1.0 M HCl solution system are 99.6% and 71.8%, respectively. In contrast, the other metal ions are hardly extracted under the studied conditions. The Au(III) and Pd(II) extracted in the organic phase are easily back-extracted with a 1.0 M thiourea/1.0 M HCl solution. A comparison with the conventional extractant for the Pd(II) separation, di-n-hexyl sulfide (DHS), revealed that the extraction rate of Pd(II) with MOTDA is much greater than that with DHS. The extraction percentage reached over 99% in less than a 2 min contact time. However, in the DHS-Pd(II) system, it takes about 240 min to achieve the extraction equilibrium. Furthermore, MOTDA can quantitatively extract Pd(II) up to half the molar amount of MOTDA. Therefore, MOTDA is a promising extractant for Pd(II) from the HCl solution after the removal of Au(III).

Jan 1, 2005

By Christophe Thiébaut

Keywords: Pyrochemistry, Salts Treatment, Distillation The pyrochemical purification of metal generates spent salts. When this metal is an actinide such as plutonium, the slags cannot be discarded and are thus disposed in nuclear facility. In order to handle with these slags, the decision has been taken to reduce stored quantities. The development of a pyrochemical treatment is in progress in the CEA Valduc centre. The feed salt, typically composed of various Pu and Am species contained into monovalent or divalent chloride matrix, is first oxidized to convert the actinides into oxides. Then the chlorides are separated from the actinide oxides by vacuum distillation. Temperatures higher than 750°C for monochloride salts mixture NaCl/KCl and higher than 1100°C for divalent CaCl2 base salts, are required to produce an industrial flow of vaporization. Inactive qualification of the process for NaCl/KCl base salt has been carried out with lanthanide surrogates. Then, a pilot equipment, called distillator has been designed and built for production-scale distillation of NaCl/KCl and CaCl2 oxidized plutonium salts. Industrial flows of vaporization have been obtained with this pilot equipment : about 4 g/cm²/h for NaCl/KCl at 800?900°C and 1 Pa, and more than 1,5 g/cm²/h for CaCl2 base salts between 1000?1200°C at 0.1 Pa. The last step, now in progress, is the integration of the distillator into a glove box.

Jan 1, 2005

By Emmanuel N. Zevgolis

Energy required for roasting and smelting of a nickeliferous laterite ore by the rotary kiln - electric furnace process is investigated. From this work it comes that thermal energy is about 65% of the total energy needed and the rest is electrical. Also, 61.3% of thermal energy input in the roasting step (of all combustibles fed into the rotary kilns) is used for pre - heating, 11.6% for pre - reduction and the rest (27.1%) corresponds to the energy of the remaining carbon in the rotary kiln products (i.e., calcine, dust and coatings). Carbon entering the system is used as follows: 57.9% for combustion, 37.1% for reduction and the rest (5.0%) remains unburnt. Exploitation of energy from gases of both furnaces, as well as the higher possible reduction degree, the optimum temperature of the calcine and also elimination of the excess air in the rotary kilns, improve significantly energy balance and economics of the process.

Jan 1, 2006

By Oliver Zach

To know as much as possible about the condition of the refractory material (lining thickness, slag layer, build ups, ...) in an high temperature furnace is very important due to the safety and economic impacts. The new CONSCAN system offers the possibility to measure the inner surface of an furnace, and based on this results to calculate the thickness of the refractory lining, slag layer, build ups,.... The CONSCAN System provides this results as figures and graphics. This system is also working under hot conditions so it is not necessary to cool down the furnace. Based on these results the process control and the refractory lining concept could be optimized for maximum campaign life of the furnace.

Jan 1, 2006

By M. N. H. Khan

CSIRO has been experimenting with supersonic flows as a method of rapidly quenching metallic vapours. Cooling rates above 106 °C/s have been achieved. The supersonic flow conditions are achieved by adiabatic expansion of the vapour through a Laval nozzle into a vacuum chamber. This paper will describe the basic physics of the process, outlining computer fluid dynamic (CFD) modelling of flow in the nozzle, the effects of different flow conditions on the condensation process and discuss the practical design issues associated with operating supersonic nozzles. Results obtained from a CFD model of the nozzle, which compared two methods of incorporating condensation, showed that inclusion of condensation substantially changes the conditions in the nozzle. Most noticeably, the effect of condensation produces a region in the nozzle where the temperature remains almost constant.

Jan 1, 2006

By Emmanuel N. Zevgolis Ismene-Polyxeni Kostika

Keywords: reduction, kinetics, laterites, rotary kiln, dust In this work, the reduction kinetics of dust from nickeliferous Greek laterites is investigated. The dust is a by-product from laterite treatment in rotary kilns and it comes from washing towers, electrostatic filters and polycyclones. Laboratory made pellets from this dust were also examined. Reducibility was studied in the temperature range of 700°C to 850°C in a laboratory tube furnace. Kinetic analysis of the results showed that at lower temperature values the mixed kinetic model verifies the experimental results of dust and pellet samples. At higher temperatures (800° and 850°C) diffusion becomes the rate controlling mechanism. The calculated activation energy values verify also the above mentioned results.

Jan 1, 2005

By Susan Jacob

The heat of fusion of silver was measured using high temperature differential scanning calorimetry (HTDSC). Heating rate, sample mass, calibration standard and cover gas flow rate were varied to determine their impact on instrument accuracy and reproducibility. Good reproducibility was achieved in most of the runs. Accuracy was not satisfactory in most of the runs, though three runs gave results within 1.7%, 3.3% and 3.5% of the literature value, within the acceptable limits. A larger mass and higher heating rate tend to generate more accurate results.

Jan 1, 2006

By Lauri E. K. Holappa

Ferrochrome, as the central constituent in stainless steels is one of the most rapidly growing primary metallic products. In this contribution results of a comprehensive study on the reduction process of chromite ore to FeCr are presented including thermodynamic examination, experimental work on kinetics and mechanisms in solid state, and smelting reduction conditions as well as kinetic modelling of solid state reduction.

Jan 1, 1999

By Dale A. Zuck

Recovery of aluminum metal from drosses? is a major factor in the recyclability success story enjoyed by the United States aluminum industry. Today's modern dross processor uses the latest technology to maximize metal recovery at the lowest cost while complying with all environmental laws and regulations. Most dross processors, however, pay little attention to the resulting saltcake, the end residual of dross recyCling, and rely on landfills for .disposition of this material.. The alternative is to recycle the saltcake, but the success of this technology is dependent on the development of reliable outlets for each of the saltcake constituents. This paper discusses the evolution of an aluminum dross oxide processing technology that ,produces an economically attractive source of alumina for the production of portland cement.

Jan 1, 1995

By M. Hochenhofer

Due to economic aspects and environmental regulations recycling of slag and waste from ferroalloy production became a very important issue for the companies during the last years. The treatment of slag depends prior on the composition, especially on their content of valuable metals and impurities. The final aim should be a total re-use of these materials in the industry e.g. cement industry, pig-iron production etc.. Therefore, to reach the required physical and chemical properties for a further use, possibilities of a metallurgical treatment have been investigated. The conditioning of slag with a high V-, Mo- and P-content via reducing metal bath showed to be one alternative. To determine the optimal process parameters, practical investigations with different slag compositions and thermodynamic calculations were carried out.

Jan 1, 2006

By Emma Arakelova

An increase in concentration of a Zn-containing volatile complex for synthesis of ZnO films was investigated when processing their target by ultraviolet radiation emitted by mercury lamp. The experiments were carried out using a flow-type quartz reactor. ZnO tableted target was preliminarily irradiated during 2 to 7 hours. H2O2 (98%) vapor at 25Pa passed through the reactor with ZnO target at 373K. As substrate material, five subsequent quartz cylinders were used at 423K. The experiment lasts 4 hours. H2O2 decomposition on ZnO surface was accompanied by formation of a Zn-containing volatile complex which passed in gas phase and decomposed on the substrates with isolation of final ZnO. The concentration of the Zn-containing volatile complex (N) in gas phase increases with UV pre-irradiation time (t) (without irradiation N = 1.05 1011 particles/cm3; after t=2 hours, N = 5.19 1011 particles/cm3, after t=4 hours, N = 9.95 1011 particles/cm3; after t=7 hours, N = 1.86 1012 particles/cm3.

Jan 1, 2006

By Andrey V. Tarasov

To carry out a physicochemical substantiation of a transition to ?soft? modes of reduction of calcine obtained by desulfurizing roasting of nickel concentrate produced as a result of copper-nickel converter matte separation in a nickel anode production circuit, an analysis has been conducted of the macrokinetic behavior of actual calcine samples in the presence of gaseous H2-CO mixtures and solid reductant additives. Within a temperature range of 900°C to 1100°C the main regularities typical of the calcine reduction process with individual gases (H2, CO) also take place when using a gaseous mixture. Under the conditions of low-temperature (900°C to 1000°C) nickel oxide reduction with products of fuel oil conversion in the presence of coke, the role of the latter is insignificant from the technological viewpoint. As a result of the present investigations, we have obtained analytical expressions of macrokinetic parameters of the reaction interaction within the [NiO] calcine-H2-CO-C-CO2-H2O-O2-N2 system.

Jan 1, 2005

By Pengfu Tan

One copper Isasmelt furnace has been operated in Xstrata Copper at Mount Isa in Australia since 1992. A thermodynamic model and computer program, CuModel, has been developed to model the distribution behaviors of Cu, Fe, S, O, Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag, copper loss in the slag, and heat balance in copper smelting process, matte converting process and copper continuous smelting process. The thermodynamic model has been used to model the key parameters in the control of the copper Isasmelt furnace. The effects of the process parameters on the control of the copper Isasmelt furnace have been predicted and discussed. These process parameters include SiO2/Fe, matte grade, coal, temperature, spec air of feed, oxygen enrichment, and MgO contents in slag.

Jan 1, 2006

By Jacques J. Eksteen

Metallurgical accounting around toll treatment smelters pose a number of challenges. This paper reviews the requirements for good sampling practice, and how conflicting requirements for good furnace operation and design often makes reliable closure of the metallurgical balance tenuous at best. Typical physical causes of variance and bias will be identified. The propagation of error (in the form of variance) will be discussed for a copper smelter.

Jan 1, 2006

By Yavuz Ali Topkaya

Rare earth ferrosilicide is a versatile alloy mainly used to control the detrimental effects of sulfur in steel and to modify graphite structures in cast iron. The aim of this study was to determine the optimum conditions to make rare earth ferrosilicon alloy using a preconcentrate produced from a bastnasite type of ore present in the Beylikahir-Eskisehir region of Turkey. This concentrate contained 23.5%REO, 41.37% CaF2, 10.69% BaSO4, 8.50% CaCO3, 4.18%Fe2O3, 2.83% Al2O3, 2.74% SiO2, 1.20% P2O5 and small amount of other oxides. The initial metallothermic reduction of this concentrate using ferrosilicon and aluminum in a graphite crucible placed in a muffle furnace gave very low recoveries due to the difficulties encountered in adjusting the slag composition, temperature and amount of additives. Therefore, two batches of rare earth oxide concentrate containing 61.1% and 81.7% cerium oxide, respectively, that were procured from a Turkish glass producer, were used to optimize with respect to temperature, duration, slag-making additives and amount of reducers. In these experiments, smelting and reduction was done in an induction furnace with graphite crucible, and, ferrosilicon and aluminum were added after melting the charge. As a result, there was no difficulty in obtaining a rare earth ferrosilicon alloy containing 35-55% RE, 5-25% Fe and 20-40% Si, with about 80% metal recovery. When the optimum conditions were applied to the preconcentrate, alloys of similar compositions were obtained with 70-80% recovery. Experiments were also done with mixtures of preconcentrate and rich concentrate, and, recoveries as high as 95% were obtained. Only in this case, to increase the recovery, mixtures had to be charged to the empty graphite crucible after heating the crucible to the required temperature.

Jan 1, 2006

By Andrew Wessman

Keywords: Recycling, Electrodeposition, Recovery, Dilute, Dissolved Metal Ions In order to facilitate the recovery of pure metals from solutions containing a mixture of dissolved metal ions, a pulsed electrodeposition method was developed. Using this method, it is possible to selectively remove metal ions from solution based upon the electrochemical potential of the particular ion desired. The use of pulsed electrodeposition rather than direct current electrodeposition creates an electrodeposited material with better morphology, increases electrical efficiency of the process, and avoids problems with short circuiting between electrodes. Using this method, it is possible to recover dissolved metal ions in a purified form in one simple step, and therefore maximizes recovery of the metal ions while obtaining them in a saleable form. This method is likely to be useful in improving the recycling process for numerous complex metal mixtures and alloys.

Jan 1, 2005

By Ji-He Wei

Keywords: stainless steel, AOD refining, side and top combined blowing, mixing characteristics, water modeling The fluid mixing characteristics in the bath during the side and top combined blowing AOD (argon-oxygen decarburization) refining process of stainless steel have preliminarily been investigated on a water model unit of a 120 t AOD converter. The geometric similarity ratio between the model and its prototype (including the side tuyeres and the top lances) was 1:4. On the basis of the theoretical calculations for the parameters of the gas streams in the side tuyeres and the top lances, the gas blowing rates used for the model have more reasonably been determined. The influence of the tuyere number and position arrangement, and the gas flow rates for side and top blowing on the characteristics has been examined. The results demonstrated that the liquid in the bath underwent vigorous circulatory motion during gas blowing, without obvious dead zone in the bath, resulting in a well mixing effectiveness. The gas flow rate of the main tuyere had a governing role on the characteristics, a suitable increase in the gas flow rate of the subtuyere could improve mixing efficiency, and the gas jet from top lance could make the mixing time prolong. Corresponding to the oxygen top blowing rate specified by the technology, a roughly equivalent and good mixing effectiveness could be reached by using six side tuyeres with an angle of 27 degrees between each tuyere, and five side tuyeres with an angular separation of 22.5 or 27 degrees between each tuyere. The relationships of the mixing time with the gas blowing rates of main-tuyeres and sub-tuyeres and top lance, the angle between each tuyere, and the tuyere number have been obtained.

Jan 1, 2005

By Pengfu Tan

Converter slag chemistry control has played an important role in optimizing converter operations. A thermodynamic model of copper P-S converter has been developed to predict the behavior of magnetite in the converter slag. Predictions of bath temperature, slag and matte compositions, and magnetite content in the slag have been validated by industrial data. The effects of fluxing strategy, returns and skim charges, oxygen enrichment, and temperature on the magnetite formation in the slag have been predicted and discussed. Some improvements of the industrial operations have been presented.

Jan 1, 2005