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By A. V. Tarasov

A flow-sheet for waste-less processing of spent lead batteries comprises mechanized separation of batteries, smelting of the metallic fraction in a kettle, electrothermal smelting of oxysulfate fraction, refining of crude lead and processing of reverts to produce commercial products. Smelting of lead-containing fraction is performed in an electrothermal furnace using a processing technology developed in the Gintsvetmet Institute and differing from conventional processes by the fact that it does not require any fluxing agent (soda); no matte is formed in the process and the amount of slag produced is minimal, because its formation depends only on the ash content of coke and the quality of battery scrap separation. The process has been patented. It has been introduced on a commercial scale in 1.8 MVA furnaces at the plant of A0 "RyazTsvetmet" (Ryazan, Russia). The process has the following main advantages as compared with conventional shaft-furnace smelting and smelting in a short-drum furnace: the process does not require technical-grade oxygen, the amount of process gas generated is minimized ensuring a decrease in lead-containing dust and sulfur dioxide emissions by 3 to 5 times per unit of lead recovered; a decrease in dust entrainment resulting in lower amounts of recycled dust; lower slag yield (a decrease from 20-25% to 3-5%); lower coke requirement (a decrease from 10-14% to 3-4%). Refining of crude lead is performed using conventional technology but there are several unique features for which know-how is available. Processing of by-products of electrothermal smelting and secondary lead refining (slag, drosses, skimmings) and ebonite fraction (crushed battery casings) is performed in a slag-fuming furnace.

Jan 1, 2002

By Rodney T. Jones

Mintek has developed and piloted a novel process for the treatment of nickel-copper and PGM (platinum group metal) sulphide concentrates. The ConRoast process is based on the removal of sulphur by roasting, followed by smelting of the dead-roasted concentrate in a DC arc furnace using an iron-based alloy as a collector for nickel, copper, cobalt, and PGMs. The environmental benefits with respect to sulphur emissions are considerable, in that essentially all of the sulphur is removed from the enclosed roasting equipment in a continuous stream of SO2 of an appropriate strength for feeding to a sulphuric acid plant. This process allows great flexibility with respect to the selection of ore types, and does not impose limits on the minimum quantities of contained base metals or sulphur, and can tolerate very high contents of chromite in the concentrate. The furnace alloy is water-atomized prior to leaching. Iron may be rejected from the alloy hydrometallurgically, by precipitation as hematite for example. The ConRoast process achieves very high metal recoveries, and produces high-purity metals, and a clean high- grade PGM concentrate.

Jan 1, 2002

By J. Chen Kuriyama

One method to store hydrogen effectively involves the use of metal complexes such as the alkali-element aluminum hydrides. The hydriding/dehydriding properties of these materials depend on how to prepare them with different structures and microstructures. The present work focused on a high-energy ball milling technique to produce Ti-doped lithium tetrahydridoaluminate (LiA1H4) and lithium hexahydroalanate (Li3AIH6) powders with nanocrystallites. The phase structures and dehydriding/rehydriding characteristics were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller measurement, thermogravimetry, and differential scanning calorimetry. The mechanism of dehydrogenation and rehydrogenation was also examined by means of X-ray photoelectron spectroscopy (XPS). The results on the relation between the reversible hydrogen storage and catalysis function of the Ti-doped complex hydride indicate that both the homogenous distribution of Ti+AI nanoclusters and the Ti¬catalyst with Ti e> Ti3+ (Ti0/Ti2+/Ti3+) defect sites play important roles in optimizing the reversible hydrogen storage.

Jan 1, 2002

By N. Kanari

The thermal decomposition studies of two zinc basic carbonate samples were carried out up to 400 "C by thermogravimetric analysis, boat experiments and differential scanning calorimetry measurements 'DSC'. The initial samples and the solid decomposition products were analyzed by scanning electron microscopy, x-ray diffraction and laser particle size analyzer. The thermal decomposition of both samples started at about 150 "C and the rate of decomposition became significant at temperatures higher than 200 "C. The apparent activation energies 'Ea' in the temperature range 150-240 "C for sample decomposition were between 132 and 153 kJ1mole depending on the sample origin. The XRD analyses of the intermediately decomposed samples and the DSC results up to 400 "C suggest that the decomposition reaction probably occur in a single step.

Jan 1, 2002

By Ki Bui Ma

Momentum wheels with superconducting bearings can integrate both attitude control and energy storage functions, with attendant savings in the total volume and weight of hardware, and power consumption, all of which are in short supply on mini-satellites. We have built and tested a prototype with a wheel of mass 1.9 kg, diameter 3.25 in, and height 3 in, which can store 3.5 J-sec of angular momentum and 5 kJ of energy when it rotates at an angular speed of 15000 RPM. The energy density of 2.5 kJ/kg achieved is comparable with the lower range for lead-acid batteries. To show that the wheel is energy efficient, we have performed spin down tests and measured the input power required to sustain rotational speed. Results indicate that power consumption, even accounting for the needs of cooling system, is significantly smaller than that for state of the art commercial reaction wheels.

Jan 1, 2002

By Kimio Itagaki

Thermodynamics and rate process fundamentals are two of the important principles involved in nonferrous production processes. The process configuration establishes whether thermodynamics or rate process behavior is most relevant in a particular application. In this paper, thermodynamic theory and rate process fundamentals are used to analyze the main characteristics of smelting and converting processes. The effect of increased oxygen potential .is examined with emphasis in view of the increased use of highly oxygen-enriched gas in modem smelting processes. Phase equilibrium and the distribution of minor elements between copper or nickel matte and FeOx-SO2- or FeOx-CaO-based slag are reviewed. The use of oxygen-rich gas has no serious effects on 'the recovery of valuable copper and silver in the matte phase, while the recovery of nickel and cobalt is adversely affected. The oxygen content in the gas also strongly affects the distribution behavior of arsenic, antimony and bismuth. Analysis of the rate processes occurring in the shaft of flash smelting, and converting furnaces by a 3-D computational fluid-dynamics model is also discussed. After being validated with experimental data collected in a large laboratory furnace, the computer model has been used to simulate the main features of an industrial flash converting operation. The results present quantitative features of the improved mixing of the particle-gas suspension and increased oxygen efficiency obtained with a distributor-cone burner compared with those with a single axial entry burner. The role of basic principles in the engineering analysis of high-intensity matte smelting processes is also discussed.

Jan 1, 2002

By Yasumasa Hattori

Fluid flow in a flash furnace concentrate burner was investigated quantitatively in order to improve burner performance. Computational fluid dynamics was utilized for researching fluid flow in a burner port mathematically then its results were reviewed in the commercial flash furnace burner and its calculation results were found to be in good agreement with the actual measurement results. Based on those results, a mathematical fluid flow model for the Sumitomo flash furnace concentrate burner has been developed so as, to improve premixing and combustion efficiency of concentrate in the reaction shaft.

Jan 1, 2002

By F. Sakurai

The enlarged Mitsubishi process in Naoshima has been in steady operation since. May 1991. However, the sulfuric acid plants have been in operation for more than 30 years. The acid plants were modernized between 1999 and 2001 by renewing some of main equipment such as the drying tower and gas heat exchangers, and introducing new technology. At the same time, as an electric energy saving measure, the electric power consumption in the sulfuric acid plant was vastly improved by decreasing the volume of gas treated the installation of low temperature activity catalyst in the 1st pass of the converter and optimization of main gas blower runner. Furthermore, last year, the oxygen plant was replaced and enlarged, and anode production increased from 240,000 to 280,000 tonnes per year with an associated increase of sulfuric acid from 550,000 to 660,000 tonnes per year. This paper describes these recent improvements in the acid plant at Naoshima smelter.

Jan 1, 2002

By A. V. Tarasov

The lack of technology for processing of sub-grade ore concentrates and intermediate products for extraction of Zn, Pb, Cu and precious metals at the metallurgical stage was a constraint for an increase in the production of these metals. The technology developed in the Gintsvetmet Institute is based on an improved electrothermal smelting process for treating calcined charge, ensuring thereby a reduction in power requirement and improving the environmental performance of the process. Electric smelting of sub-grade polymetallic concentrates produces lead bullion, to which the bulk of gold and silver reports, as well as well segregated matte and slag concentrating the bulk of zinc. Lead bullion and matte are commercial-grade products; zinc is recovered from high-grade (15% Zn) slag by slag fuming process. Reduced loss of precious metals in slag ensured by the given technology is attributed to the fact that the slag contacts with matte with low contents of gold, silver and lead, rather than with lead bullion. Limited amounts of off-gas typical of electrothermal processes ensure cost-effective operation of dust recovery devices and a reduction in emissions of harmful pollutants into the ambient air.

Jan 1, 2002

By Grégory Miette

The paper deals with a process that allows the recycling in a cupola of EAF dusts with 18 % Zn. It produces dusts with zinc grade higher than 50 - 55 % and commercial cast iron with less than 200 ppm Zn, 50 ppm Pb, 0.15 % S. The paper focuses mainly on lab tests made with the aim to develop an effective formulation of self reducing - melting pellets. With such a formulation, agglomerates develop a breaking load higher than 125 - 150 kg without any thermal treatment. Zinc and lead are volatilized in the cupola with yields higher than 95 % at 1200 OC, before any melting. Sulphur is transfemed into gas and slag. All these conditions allow to lower zinc, lead and sulphur grades below the cast iron specifications. Results of first bench scale tests performed at Fonderie Piret to validate the process will be presented.

Jan 1, 2002

By K. Noda

Tamano Smelter of Hibi Kyodo Smelting Co., Ltd. is carrying out a low cost production using a Tamano Type Flash Smelting Furnace (T-FSF), which is an improved version of Outokumpu Type Flash Smelting Furnace but without slag cleaning furnace and also by developing its own coke combustion technology. Coke combustion technology that is the basis of the system has been improved several times and, at present, it has evolved to a stage where it can be reproduced on the Computer guided system for Coke Combustion in the T-FSF (CCCT) using a general- purpose computer. This CCCT is featured by 'its trend control and predicting function, and an operator can freely control the operation parameters so as to control the operation flexibly. We have recently developed an overall energy reduction system covering the Smelting Plant to Sulfuric Acid Plant, which we call an Optimum Low Cost Operation System (OLCO) to reconsider the energy costs including coke, heavy fuel oil, and electric power. In this report, we would like to present the recent operation of T-FSF based on CCCT as well as the optimum energy operation utilizing OLCO system.

Jan 1, 2002

Rotary kiln incinerators are widely used in the incineration of various types of hazardous wastes. However, the complex transport processes within the incinerator are not well understood. Due to large variations in waste types and difficulties in feed characterization, the incineration process meets great challenges in a smooth operation, and expects uncertainties in the process chemistry and emission control. In order to get better understanding of the incineration process, process simulation was made on the kiln behavior by using Computational Fluid-dynamics (CFD) to characterize gas flow, temperature distribution and waste combustion in the incinerator. Temperature measurement was conducted in an operating incinerator to validate the CFD model. This paper addresses the environmental issues related to the hazardous incineration process, and reports the recent simulation results on gas flow and mixing, combustion heat transfer, and potentials to reduce emissions.

Jan 1, 2002

By M Kolbe

Co-Cu exhibits a metastable miscibility gap in the region of the undercooled melt. Specimens have been undercooled and solidified containerlessly into the metastable miscibility gap in an electromagnetic levitation facility (EML) and in drop tube (DT) experiments. Due to the high undercooling the velocity of the solidification front is very high and the microstructure is frozen in instantaneously. The microstructure of samples processed in the EML is influenced by the electromagnetic stirring due to the induction of electrical currents into the melt. A variety of microstructures has been observed. After undercooling below the binodal the liquid melt separates into the Co-rich L1-phase and the Cu-rich L2-phase. Two basic morphologies of the L1-phase can be observed, they can be attributed to the transition in dendrite growth from diffusionally and thermally controlled to only thermally controlled growth. Transient microstructures are observed after solidification in the vicinity of the binodal. Drop tube experiments, which lead to a rapid solidification of a distribution of droplets under reduced gravity conditions, in contrary allow for the observation of the early stages of demixing: the microstructure shows a homogeneous distribution of spherical particles of the minority phase in the droplets. The cooling rate of the droplets and its dependence on the droplet radius has been calculated. The solidification velocity as a function of undercooling has been measured in the EML for the composition Co-lB.Bat%Cu. The data are analysed in the framework of the LKTlBCT model with a velocity-dependent distribution coefficient as well as within a model of Galenko and Danilov using a kinetic growth coefficient of u=0.22 m/Ks.

Jan 1, 2002

By Vitalij K. Pecharsky

Recent interest in complex aluminohydrides as potential near ambient, ultra-high capacity, solid-state sources of hydrogen (e.g., for fuel cells) calls for an improved understanding of the processes occumng in these hydrogen-containing materials during both the release and the uptake of hydrogen. Lithium aluminohydride (LiAlH4) rapidly releases 5.2 wt. % of hydrogen (i.e., nearly four times more than LaNis-based alloys) during mechanochemical processing at ambient conditions in the presence of transition metal catalysts. Using a variety of solid-state characterization techniques, the mechanochemical transformations in a series of LiAlH4 - metal catalyst systems have been examined and preliminary insights on the mechanism have been obtained. Surprisingly, the well-known hydrogenating-dehydrogenating catalysts, such as Ni and Pt, are practically inactive in the mechanochemical dehydrogenation of LiAlH4.

Jan 1, 2002

By U B. Pal

Downsizing and decommissioning of nuclear facility operations is increasing the stockpile of various different grades of Radioactive Scrap Iron (RSI). Disposal of this material not only represents significant resource and value lost, but also necessitates long term monitoring for environmental compliance. The latter results in additional recurring expense. It is desirable to be able to decontaminate the RSI to a very low level that can be recycled or used for fabrication of containers for RSI disposal instead of using virgin metal to fabricate the container. Electro-Slag Remelting and Refining (ESR) is often used for decontaminating radioactive contaminated sources of scrap iron such as stainless steel. Non-radioactive oxides of cerium are used to simulate the radioactive oxide contaminants of Uranium and Plutonium. The success of the ESR process is strongly dependent on the capacity of the slag to rapidly incorporate the radioactive contaminant (simulant). In this study we have measured the slag-metal partition coefficient for cerium and investigated the reaction mechanism for the dissolution CeO, in the slag.

Jan 1, 2002

By E. Dendy Sloan

An overview of hydrate properties is given, with emphasis on unusual deviations from ice, the most common solid water form. Reliable sample preparation and reproduction of in situ hydrates provide the foundation for all hydrate science and engineering. Relations are given to connect the three domains in the title: (1) micro-scopic properties measured with Raman, NMR, and diffraction spectroscopy, (2) meso-scopic properties measured with single crystals, and (3) macro-scopic properties measured with pressures, temperatures, volumes, etc. A principal illustration relates micro-scopic and macro-scopic domains. Experiments provides the basis for improving statistical thermodynamics model for these compounds. To date, this model is one of the most commonly used industrial statistical thermodynamics applications, based upon the classical model of van der Waals and Platteeuw (1959). Microscopic measurements and simulations indicate model assumption improvements, resulting in the next generation of the statistical thermodynamics for improved macroscopic property prediction.

Jan 1, 2002

By W. D. Cho

Fast dissolution of nonmetallic inclusions such as alumina particles in molten slags has been required in secondary steelmaking -ladle and tundish - to minimize the amount and the size of nonmetallic inclusions in steel products. In the present work, the dissolution behavior of alumina particles in molten CaO-A12O3 and CaO-A12O3-SiO2 slags at the temperatures between 1450 and 1550°C have been investigated in terms of kinetics and mechanism. Alumina particles were added directly into the slags and the variation of the particle size with time was determined using optical and electron microscopies. The conventional types of slag for ladle and tundish were included in the dissolution study. The effects of Al2O3, Siq, CaF2 and MgO contents on the dissolution rate of alumina particles have also been determined. The diffusion boundary layer between alumina particle and bulk slag phase has been observed and analyzed using SEM and EDS. Based on the analysis of kinetic data and the boundary layer, the dissolution mechanism has been discussed.

Jan 1, 2002

By Junji Shibata

Zeolite synthesized from coal fly ash has many intelligent properties such as cation exchange, adsorption, catalyst and so on. The suitable use of the zeolite, however, is not established in an actual commercial scale yet. From the viewpoints of an effective usage of coal fly ash and the zeolite obtained from coal fly ash, we propose the new concept for environmentally friendly usage of zeolite, in which coal fly ash safely returns to the soil with growing plants and purifying wastewater. This method can make great contribution to recycle of coal fly ash, to purification of high nutritious water and to tree planting.

Jan 1, 2002

By Norihiro Murayarna

Hydrothermal synthesis of K type zeolite was carried out by using coal fly ash as a raw material and KOH as an alkali source. The change in various physical properties of the obtained zeolite, such as the kind of zeolite crystal, cation exchange capacity, surface structure of zeolite and particle size distribution were investigated through the overall reaction of zeolitization. The reaction mechanism of K type zeolite from coal fly ash was investigated from these results in this study

Jan 1, 2002

By Zhijing Zhang

The management of hazardous wastes is important in a society which is increasingly concerned with environmental issues. Incinerators such as the slagging rotary kiln are widely used in the treatment of hazardous wastes. However, in order to assure a smooth operation of the rotary kiln, the melt should have both a low melting point and high fluidity. In this study, the fluidity of various hazardous waste rotary kiln slags was measured in terms of length of flow using the crucible test technique. It was found that the slags have melting points ranging from 1372 to 1424°C while their fluidities varied from 61-102 mm. The effect of addition of oxides on the fluidity of a slag containing 47 wt% SiO2 was also investigated. For this slag, additions of SiO2 (up to 56 wt%), FeO and Na20 increased fluidity, whereas the addition of CaO and A1203 resulted in lower fluidity values.

Jan 1, 2002