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By C. J. N. Buisman

THIOPAQ technology developed and marketed by PAQUES Bio Systems in Balk, Netherlands, has been successfully used at commercial scale at the Budelco zinc refinery in the Netherlands for the treatment of contaminated groundwater since 1992. In essence, THIOPAQ technology consists of two biological process steps in series: sulfate reduction to hydrogen sulfide (anaerobic) and sulfide oxidation to elemental sulfur (aerobic). The biogenic sulfide produced can be employed for the chemical precipitation of metals in solution either inside the anaerobic reactor or in a separate vessel. Since the solubilities of most metal sulfides are much lower than of their respective hydroxides, considerably lower effluent metal concentrations can be achieved with THIOPAQ systems than in neutralization processes which immobilize metals predominantly by hydrolytic precipitation. In recent years, PAQUES has made significant advances in the design and operation of aerobic and anaerobic bioreactors for metal-sulfur systems. Moreover, the company has increased its technology portfolio to allow the development of more process oriented applications of THIOPAQ technology. A new PAQUES designed plant at Budelco treating sulfatecontaining proceswaters will be started up in 1999. The sulfate reduction is accomplished in a 500 m3 reactor in which hydrogen is used as electron donor. The endproduct, ZnS, is used for Zn and H2S04 production.

Jan 1, 1999

By Cody Burcher-Jones

The recovery of rare earth elements (REEs) through heap leach/in situ techniques from so-called ion adsorption clays (IACs) is attractive due to their inherent simplicity. However, the underlying mechanisms of these processes are poorly understood. In this study, the deportment of REEs in a typical IAC material has been investigated and was found to concentrate in the phyllo-layers of the clays, especially hallyosite, and was readily desorbed by various ion-exchange reagents indicating various potential routes to liberate them. Here we are reporting the use of seawater (0.5 M NaCl), spiked with various amounts of (NH4)2SO4, and found better extraction using a reagent mixture than NaCl on its own. Further, the leaching of REEs from a bed of clay material was investigated over time to understand the rate of transport through the stagnant material. Results indicate that REE release is likely to be controlled by diffusion through the clay material, while desorption in agitated systems is rapid. A degree of fractionation between different REEs can be observed during diffusion. Nonetheless, the successful operation of in situ leach operations for this type of material would depend primarily on how easily solution cocktails can be made to flow through the bed material.

By Sung Wng Kim

The binary antimonide compounds with the skutterudite structure have a potential for thermoelectric applications because of the high carrier mobility, high thermoelectric power, and relatively low thermal conductivity due to the complex crystal structure. However, the room temperature thermal conductivity of these skutterudite materials is as high as about IOW/mK with an estimated 80-90% contribution from the lattice thermal conductivity. Because the lattice thermal conductivity of related ternary skutterudite compounds can be substantially reduced due to the additional phonon scattering, a study of thermoelectric properties of these compounds is of interest. The binary IrSb3, ternary Ir1.xRuxSb3 and Ir(MxSb1.x)3(M=Ge, Sn) compounds were prepared by hot pressing of pre-reacted powders. We have measured the electrical resistivity, thermoelectric power, and thermal conductivity, in a temperature range from room temperature to 973K. The binary IrSb3 compound is found to have P-type electrical properties exhibiting a good Seebeck coefficient (up to 225µV/K around 773K), electrical resistivity(5x10-5Ohm M around 933K), and relatively low thermal conductivity(6W/mK around 950K). The lattice thermal conductivity, K[2] was calculated from the Wiedemann-Franz relationship.

Jan 1, 2002

By V. A. Bryukvin

It has been found that by superimposing symmetric alternating current over the process, the rate of nickel and cobalt leaching from metallized products with copper sulfate solutions increases by a factor of 1.5 to 2.0 and the apparent activation energy of the process investigated is reduced from 12 down to 6.6 kcal/mole. It appears especially attractive to use alternating current for anodic dissolution (oxidation) of metallic scrap of refractory metals and their alloys in ammonia electrolytes permits production of high-grade commercial products in the form of respective ammonium salts using a short and virtually reagent-free process flowsheet. Similar approaches can be applied also for electrochemical processing of nickel and copper scrap in sulfuric acid media with subsequent recovery of pure sulfate salts or electrolytic processing. Electrochemical technology for recycling of tungsten-cobalt (WC 15) and tungsten-rhenium (WR 20) alloys has been also investigated. In the former case, anodic oxidation of carbide alloy was carried out in nitric acid electrolyte with production of pure tungstic acid. The research conducted has indicated that the physicochemical effect of alternating current results in a lower activation energy of electrode reactions due to changes in the mechanisms of the electrode reactions themselves.

Jan 1, 2006

By E. J. Peuraniemi

Recently commissioned Kennecott-Outokumpu flash converting was developed to replace the approved but environmentally outdated Peirce-Smith -converting to satisfy the globally tightening emission regulations. In the present study, dust formation and reaction mechanisms of two copper mattes with different experimental parameters were studied in lean suspension conditions. Both mattes had very high copper content of approximately 75 wt% and low iron content of 4.5 wt% and 1.2 wt% Fe. A laboratory scale, vertical laminar-flow furnace with a low feeding rate was used to simulate the phenomena taking place in the reaction shaft of a flash converter. Experimental conditions included temperature of 1300 °C with reaction gas oxygen contents of 20 vol%, 50 vol%, and 75 vol%. In the experiments, sieved particle fractions were fed to the furnace and sampled after short reaction time intervals by quenching them into a water film. Collected particles were analysed chemically for their main elements to define their removal rates. Also, optical and scanning electron microscopy with EDS-analyser were applied to determine phenomena occurring during reactions. Kinetics of oxidation as well as ignition of particles are discussed. Changes in particle morphology, size, and composition are reviewed to describe dust formation and reaction mechanisms.

Jan 1, 1999

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 C. G. Anderson, L. G. Twidwell

"Throughout the world, there are many orebodies or materials which have significant value but also contain arsenic, antimony, and mercury. As regulations on the transport, exposure, disposition and emission of these elements have become more stringent; it has become increasingly more difficult to derive the values from the resources. This paper outlines the fundamentals of alkaline sulfide hydrometallurgy and its successful application to arsenic, antimony and mercury bearing ores, concentrates, by-products, and other materials.Fundamental Alkaline Sulfide HydrometallurgyHydrometallurgical methods can be employed for treatment of gold, arsenic, antimony, tin and mercury containing materials, concentrates and ores as well as complex ones containing any number of metals. The alkaline sulfide system is one of these and is essentially a mixture of sodium sulfide and sodium hydroxide. This is a unique hydrometallurgical system as it is a very selective lixiviant for the distinct leaching of tin, gold, antimony, arsenic and mercury [1-7]. Worldwide, it is employed industrially in the CIS, China and the United States for the production of antimony [8-15].As an example, when the system is applied to an arsenic containing material like orpiment, As2S3, a solution of sodium thioarsenite is formed. This is illustrated as:"

Jan 1, 2008

By A. V. Tarasov

In order to improve the efficiency of hydrometallurgical processing of pyrrhotite concentrates, an integrated set of research has been carried out to investigate the use of sulfur dioxide in individual unit operations and as a leaching agent in the autoclave process as a substitute for oxygen. Treating iron-containing raw materials for production of nonferrous metals are based on the selective reaction of SO2 with iron sulfides and oxides. Iron is dissolved as sulfate, which can be treated in a separate circuit to produce iron-containing pigments or it can be disposed of after neutralization. Nonferrous and precious metals contained in pyrrhotite concentrate do not react with sulfur dioxide and remain virtually completely in the solid phase, i.e. high-grade sulfide concentrate to be treated by hydro- or pyrometallurgical methods. Elemental sulfur formed in the process of leaching is separated from the pulp in granulated form as a result of the use of special surfactants. The process of sulfide concentrate leaching with the use of sulfur dioxide is conducted at temperatures above the sulfur melting point (119°C) with distributed feeding of surfactant and under a partial pressure of sulfur dioxide of up to 0.3 to 0.5 MPa.

Jan 1, 2006

By H. Y. Cheng

A pulse column solvent extraction system was evaluated as an alternative to mixer-settlers for the separation and purification of rare earths. The column tested had an inside diameter of 44.5 mm and had 36 sieve plates with a free area of 25%. Pulsing was provided pneumatically using a solenoid valve controlled by a timer so that both pulse amplitude and frequency could be varied. Feed to the column was a mixed rare earth chloride solution containing 10 g RE L-1. The extractant was 5% Ionquest® 801 in Shellsol 2037 diluent. Hydraulic performance of the pulse column was excellent with no propensity towards stable emulsions or crud formation under normal operating conditions. The column was operated in organic-continuous mode with flow rates chosen so that yttrium and the heavy rare earths were extracted with high efficiency while the light rare earths were rejected. Yttrium extraction varied from 83 to 99.2%. Concentration profiles were measured in both the aqueous and organic phases, and, from this data, the height of a transfer unit (HTU), the mass transfer coefficient (Kxa) and the continuous-phase axial dispersion coefficient (Ey) were computed. The HTU ranged from 17-92 an which is within the range of values reported for other (non rare earth) pulse column systems.

Jan 1, 1992

By Oleg I. Platonov

Method of high-temperature reduction of oxygen-bearing sulfurous gas has been developed at Copper Plant (CP) of MMC ?Norilsk Nickel? Trans-Polar Division (PD) with the aim of producing elemental sulfur from Vanyukov furnace? off-gas. Non-explosive reduction technology of oxygen-bearing sulfurous gas by methane utilized at Copper Plant has been designed to separate the processes of gas heating and sulfur dioxide reduction based on different kinetic of the reactions oxygen fixing and SO2 reduction. First, natural gas promptly reacts with oxygen contained in the process gas to heat a gas mixture up to the temperature of sulfur dioxide reduction (1200C). Then isothermal reduction takes place within 1 sec. Combustion chamber (pre-chamber) design developed based on the above principles is presented. Practical experience of the two reduction reactors operation at CP since 1996 proves high efficiency of the developed reduction process. The volume efficiency rises dramatically thanks to the fact that both fuel and reducing agent are fed into the reactor volume in the form of high-speed turbulent jets providing an intensive mixing of the reacting gases. On condition of equal internal volume of the reactors, the developed process offers higher efficiency of reagent interaction resulting in sulfur conversion exceeding 90%, as compared to the equilibrium one.

Jan 1, 2006

By G. St-Amant, V. Cloutier, E. Ghali, S. Jin, G. Houlachi

During the casting of lead-silver anodes, variations in cooling rates result in the formation of an uneven microstructure. The slowly cooled areas (SCA) have a coarser microstructure than that of the remaining part (called "the general zone"). The effect of anode microstructure on the electrochemical behavior was investigated using galvanostatic, potentiodynamic and electrochemical impedance techniques. The results show that the resistances for the two steps of the oxygen evolution reaction on the slowly cooled areas of Pb- Ag anodes are higher than that on the general zone. The double layer capacitance for the first step of the oxygen evolution reaction (OER) and the pseudocapacitance of the second step of OER on SCA are smaller than those on the general zone. The potentiodynamic results show that the amount of lead dioxide formed on the SCA is greater than that of the general zone of the anode. The potential decay curves after 30 minutes of galvanostatic polarization at 45 mA/cm2 show that the corrosion potential of the SCA is 200 mV lower than that of the general zone. This can lead to perforation because of the formation of a galvanic cell with a small anode and a large cathode.

Jan 1, 2000

By He De-wen

The increasing population and living standard in urban areas, have been accompanied with the growing quantity and composition complexity of rubbish, which are causing well-known social effects of pollution, while rubbish (solid waste) is a recyclable resource. To convert rubbish into useful materials, the essential measure is to carry out sorted collection of rubbish. The preconditions of implementing sorted collection are presented in the paper. 1 Characteristics of rubbish composition and amounts of recyclable contents are basic condition to implement sorted collection. 2 The existing available technologies of recycling, economic benefit from recycling, and disposal scheme of residual rubbish are restrained condition for sorted collection. 3 Public understanding and support to sorted collection are the key to success. 4 The government policies to be favorable for sorted collection is the pledge of success. 5 The establishment of a steady solid waste recycling market is also a guarantee to implement sorted collection continuously. 6 To establish management system of rubbish recycling as soon as possible. Further, the methods and procedure of sorted collection are discussed in detail and beneficial comments and theoretical basis to promote sorted collection of rubbish in urban area are presented; it will contribute reference value to municipal solid waste management.

Jan 1, 2006

By Himaki Nakano, Kenji Hara, Toshiaki Tsuru, Shunsuke Kawano, Takeshi Ohgai, Hisaaki Fukushima, Shigeo Kobayashi, Tetsuya Akiyama

"Electrodeposition of Fe-Ni and Zn-Ni alloys from aqueous solutions is one of the well-known examples of anomalous codeposition in which less noble metal deposits preferentially. In this paper, the electrodeposition behavior of these alloy systems was compared between the methanol and aqueous baths. In Fe-Ni system, the significant suppression of the deposition rate of more noble Ni was observed over a wide range of electrolysis conditions in both methanol and aqueous baths. However, the electrodeposition of Zn-Ni alloys showed the typical feature of normal type codeposition in the methanol baths, which was completely different from that in aqueous sulfate baths. The difference in the electrodeposition mechanism between Fe-Ni and Zn-Ni alloys was discussed on the basis of the alloy deposition behavior in the baths in which the activity of water was varied:INTRODUCTION'It has been well known that Fe-Ni alloys show an excellent soft magnetic property. Therefore, thin films of this alloy have been used to fabricate the'-various magnetic devices. For the production of Fe-Ni thin films, dry processes such as sputtering, PVD and CVD are 'employed frequently and the resulting films showed a preferable property as a magnetic material. Electrolyses as a production technique of thin films, on the other hand, has the advantage over other processes in its cheaper production cost due to the simplicity of the production unit The Zn-iron-group metal alloys such as Zn-Ni and Zn-Fe electrodeposited on a steel sheet ale known to exhibit excellent corrosion resistance and therefore the electrodeposition of these, alloys has been applied to the production of surface treated steel sheets mainly for automotive body panels.According to Brenner (1), the electrodeposition behavior of Fe-Ni and Zn-Ni alloys was' classified into the' 'anomalous type. In this type of codeposition, less noble metal, i.e. Fe for Fe-Ni and Zn for Zn-Ni system, deposits preferentially and the change in -the alloy composition- with the variation of electrolysis conditions was unpredictable because of their obscure deposition mechanism. Since most properties of the alloys mainly depend on their composition, the composition of the deposited' alloys must be controlled strictly. Therefore, it is neces5al)' to clarify the mechanism of anomalous codepasition in Fe-Ni and Zn-Ni systems: Several mechanisms have been proposed so fur, and among them the hydroxide .suppression mechanism (2), (3) has been regarded most plauslble depend on their composition, the composition of the deposited' alloys must be controlled strictly. Therefore, it is necessary to clarify the mechanism of anomalous codeposition in Fe-Ni and Zn-Ni systems: Several mechanisms have been proposed so far, and among them the hydroxide suppression mechanism (2), (3) has been regarded most plausible. According to this mechanism, it can be predicted that the codeposition behavior depends greatly on the characteristic of water solvent in this study, using methanol as a solvent, the electrodeposition behavior of the anomalous codeposition was investigated to discuss the validity of the hydroxide suppression mechanism."

Jan 1, 2000

By Kenichi Moriyama

The Sumitomo Toyo Copper Smelter started operation in 1971, as an epoch-making smelter at which 9996 of the charged sulfur could be captured. In the past ten years, the amount of treated copper concentrate has-been increased from 1,300 l/ day to 1;900 t/ day by the extremely effective application of the oxygen enrichment for a flash smelting furnace and converter furnace. The sulfuric acid production capacity at the acid plant has also been increased up to 1,900 t/ day corresponding to the increase of copper concentrate smelting rate without installing an additional acid plant. Furthermore the sulfur fixed ratio is kept at a high level, more than 99.996. despite the SO. strength fluctuation of the wide range of 596 to 1396 which is attributed to the combination of flash smelting furnace and, P.S. converter. These -operational results at the? acid plant were achieved by several modifications. and two examples are briefly described as follows; (1) Converter modifications in order to cope with the high SO, strength -gas (2) Introduction of the anodically protection shell and tube type acid coolers In addition. the quality of sulfuric acid has been positively increased. For example, the concentration of iron and arsenic, which were the main Impurities in ?sulfuric acid, was successfully .reduced.

Jan 1, 1995

By Dinesh Agrawal

Microwave energy has been in use for variety of applications for over 50 years. These applications include communication, food processing, wood drying, rubber vulcanization, medical therapy, polymers, etc. In the last two decades microwave heating has been also applied very effectively and efficiently to heat and sinter ceramic materials. Microwave heating is recognized for its various advantages, such as: time and energy saving, very rapid heating rates, considerably reduced processing cycle time and temperature, fine microstructures and improved mechanical properties, better product performance, etc. The most recent application of microwaves has been in the field of metallic materials for sintering, brazing/joining and melting. Several common steel compositions, pure metals and refractory metals have been sintered in microwaves to nearly full density with improved mechanical properties. Many commercial powder-metal components of various alloy compositions including iron and steel, copper, aluminum, nickel, Mo, Co, Ti, W, Sn, etc., and their alloys have also been sintered in microwaves producing better properties than their conventional counterparts by using a 2.45 GHz multimode microwave system. This work has been further extended to join and braze bulk metal pieces, especially super alloy based turbine blades. Further, in a specially designed microwave cavity, even the bulk metals can be made to couple with the microwave field and melted. The implications of these findings are obvious in the field of powder metal technology.

Jan 1, 2006

By Dachun Liu, Wenlong Jiang, Baoqiang Xu, Yongnian Dai, Bin Yang

"In the traditional method for refining of indium, glycerin-KI and glycerin-NH4Cl are used as electrolytes to remove Cd and Tl by electrolytic refining, which produces In with a purity of 99.995%. Large quantities of polluted industrial waste water are the result. It is calculated that the saturated vapor pressure of Cd and Tl are between 1-200 Pa, which is much larger than the vapor pressure of In. Thus, the study of removing Cd and Tl was carried out over the temperature range between 700-950 °C and pressures between 1-15 Pa. After vacuum distillation the contents of Cd and Tl in crude indium could sharply fall below 1 ppm..IntroductionIndium is a is a pale blue and silver white metal, and has high ductility [1-2]. Pure indium is generally used as a raw material to produce semiconductor compounds, fluorescent material and ITO targets [3]. Sublimation, zone melting and electrolytic refining are major methods to produce pure indium from crude indium. Electrolytic refining is the main method to product pure indium at present. High productive efficiency, simplicity of operation and short cycle of production are major advantages. However, glycerin-KI and glycerin-NH4Cl are used to remove Cd and Tl in electrolysis method. Large quantities of polluted industrial waste water are the result[4]."

Jan 1, 2012

By C. O. Bounds

The magnetic properties of (NdDy)15Fe78B6 sintered magnets have been evaluated using powder prepared by Inert gas atomization. The atomized powder had a particle size distribution from 1 to approximate 1000 microns. The as atomized powders have been sieved into, coarse, intermediate, and fine fractions; magnetic properties were evaluated for the as produced powder and each fraction. A B, of 11.7 kG, a Hci of 11.0 kOe and a BHmax of 32.5 MGOe was -obtained on a sintered magnet made from the as-atomized powder. The magnet made from coarse powder exhibited a slightly higher B, of 12.1 kG, while that from fine powder showed a decrease in B, to 11.2 kG. Hydrogen decrepitation has been utilized to study its effect on the magnetic properties. Finally, cast ingots with a definite columnar structure have also been used to compare the magnetic properties of magnets of the same nominal, composition but of different alloy preparation process. Hydrogen decrepitation does not appear to improve the magnetic properties of magnets made from thin cast ingots. However, it does show a significant improvement in the Hci of magnets made from the atomized powders. Possible causes for the differences in the magnetic properties on magnets made from each process have been discussed in the paper.

Jan 1, 1992

By Fernando Guevara

Many smelting and slag-cleaning furnaces operate with cooling systems designed to freeze a slag layer over the refractory to protect it. The fluid flow and heat transfer conditions associated with the freeze layer and mushy zones are poorly understood. These phenomena were simulated with a small-scale room temperature, 2-dimensional model, using an aqueous solution of calcium chloride to simulate the slag. Reasonable similarity with conditions encountered with copper and nickel smelting systems was achieved (Pr 50 and Ra 108, in the laminar-turbulent transition). Measurements of the freeze layer development and velocities were made with the Particle Image Velocimetry (PIV) technique. Direct Numerical Simulations (DNS) were also made of the unsteady fluid flow and heat transfer problem. It was found that the solidification process is well described using an improved model for high molecular viscosity in the mushy zone. Solid front growth, isothermal profiles, velocity profiles and heat transfer through the walls showed good agreement between the PIV and DNS results. Experimental and numerical velocity profiles close to the freeze layer show a parabolic behaviour in the vertical velocity profile which is completely different from the calculation of heat transfer using a sharp interface model. The reason for this is attributed to the effects of the mushy zone with a high viscosity and high shear stresses acting on that area.

Jan 1, 2006

By Supachai Surapunl

The distribution behavior of VA minor elements (As, Sb and Bi) in the smelting stage of the Mitsubishi process were evaluated thermodynamically based on thermodynamic data and operating data. The fractional distributions between the gas, slag and matte phases considered as the degree of vapor saturation of l.0 are as follows: 53.8, 27.2 and 19% for As, 23.6, 56.6 and 19.8% for Sb, and 91.3, l.1 and 7.6% for Bi, respectively. Arsenic is mostly distributed to the gas and slag phases. It is effectively eliminated by volatilizing and slagging. Antimony is mainly in the slag phase, which is suitably removed by slagging. Bismuth is easily vaporized to gas phase. The degree of vapor saturation has a large effect on the distribution behaviors of the three elements between the three phases. The amount of a minor element in the charge has an effect on the distribution of As but no effect on the distributions of Sb and Bi. Increasing matte grade and temperature results in the change of distributions for As and Sb, significantly. The change in the distribution ratio between slag and matte phases also considerably affects the distributions of As and Sb. The distribution behavior of Bi is not significantly changed by the change in matte grade, temperature and distribution ratio.

Jan 1, 2003

By Xiao Long, Ting Wu, Lilong Zhu, Qian Wang, Shengping He

"During the continuous casting of peritectic steel slabs, mould fluxes with high crystallization capacity are usually chosen for improving slab surface quality. However, the lubrication condition of casting shell also could be deteriorated. Since precipitation of crystals within liquid slag film can change the composition and property of liquid slag over solid-liquid slag film interface region, its impacts on continuous casting process also are not clear. In order to clear this phenomenon, an experiment method was put forward, and mould fluxes for peritectic steel slabs continuous casting were selected and examined. The results reveal that after crystals have been separated, the crystallization capacity of leftover liquid slag increased with different levels, which could deteriorate the lubrication condition of casting shell and cause a series of problems. Thereby, mould fluxes with high crystallization capacity at beginning for heat transfer control and then weaker after crystallization should be considered in the future.IntroductionIn the continuous casting of peritectic steel slabs, contradiction between heat transfer control and slab shell lubrication by mould fluxes has been treated as a key problem for maintaining a smooth manufacturing process [ 1]. Strong and uneven horizontal heat flux over the meniscus region will cause uneven solidification of casting shell, especially for peritectic steel slab with enormous volume change caused by phase transition. All of those could cause surface defects like longitudinal crack [2-4]."

Jan 1, 2013