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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

By Guo Xueyi

The dissolution behaviors of valuable metals, lead and zinc, from secondary fly ash generated in municipal incineration plants were investigated using some lixiviants: sulfuric and hydrochloric acids, acetic acid and some chelating reagents including L-asparaginic-N,N-diacetic acid (ASDA), a biodegradable, and therefore, environmentally benign novel chelating reagent. It was found that zinc exists mainly as ZnO, whereas Pb probably as PbOHCI and PbO, and the easily soluble components in SFA are KCI and NaCl. Suitable amount of HCI can dissolve all of lead and zinc from SFA. Sulfuric acid can selectively extract zinc leaving lead in the residue. Ethylenediaminetetraacetic acid (EDTA) is an effective chelating reagent to extract both zinc and lead. Although ASDA and diethylene¬triaminepentaacetic acid (DTPA) can selectively extract more than half of lead from SFA, it would by no means be regarded as highly effective reagents for the extraction of these metal values. Keywords: Lead, Zinc, Secondary fly ash, Leaching, Dissolution

Jan 1, 2002

By Karl-Heinz Daum

Outokumpu Lurgi Metallurgie GmbH, Oberursel, Germany ? give saleable by-products, ? not interfere with smelter performance, ? treat all gas streams simultaneously, and ? comply with environmental regulations. The latest developments in sulphuric acid plant design are presented.

Jan 1, 2002

By Jens Kristen Laursen

In 1999, Molymex S.A. de C.V. (Molymex), Mexico. (a company wholly owned by Molibdenos y Metales S.A. (Molymet), Chile) decided to install the Haldor Topsrae Wet gas Sulphuric Aicd (WSA) process for cleaning of the 4-5% SO2 off-gas from their molybdenum sulphide master in Cumpas, Mexico to produce sulphuric acid. The decision to install a WSA plant was based on the successful operation of a WSA plant at Molymet's molybdenum sulphide roaster in Santiago, Chile since 1993. This paper describes the process layout of the Cumpas plant, the operating experience of the Santiago plant, and the, differences in. process design between the two plants. It will furthermore summarise the applications of the WSA process for other roasting plants and smelters within the non-ferrous. metals industry producing metals such as copper, lead, and molybdenum.

Jan 1, 2002

By Robert H. Hsu

Palladium finely dispersed in a substrate of kieselguhr, Pd/k for short, has been successfully used for hydrogen storage, separation and pumping for a number of years at the Savannah River Site (SRS). Recently SRS has developed a new pd/k flow through bed (FTB) prototype for separating hydrogen from other gases and simultaneously storing the hydrogen on palladium. The FTB uses single-pass liquid nitrogen cooling during hydrogen absorption/separation/storage and electrical heating for desorption/unloading of hydrogen. Fourteen absorption-desorption or loading/unloading cycles using hydrogen have been conducted with the new FTB prototype. Test results show that all design performance objectives have been successfully achieved: recover 295% of hydrogen gas from feed gas, produce 99.9% hydrogen product gas and < 5% hydrogen in discharge gas. This paper will discuss characteristics of the palladium-coated kieselguhr or diatomaceous earth, design and operation of the FTB, and results of performance tests such as separation efficiency, hydrogen storage capacity and system heat transfer characteristics.

Jan 1, 2002

By J. Huot

It has been shown that magnesium-based metal hydrides such as Mg2Ni could be synthesized by high energy mechanical alloying. This process creates a nanocrystalline alloy that has enhanced hydrogen sorption properties due to the high density of defects and grain boundaries. Unfortunately, this process also requires a long synthesis time (up to 100 hours in some cases). In order lo reduce processing time and cost of synthesis, we have investigated the effect of milling at elevated temperature under an inert atmosphere. Milling at high temperature improves interdiffusion of the elements and reduces the number of structural defects such as vacancies, dislocations and internal strain. It was found that by milling elemental powders at 200°C. a complete synthesis of Mg2Ni could be achieved in 8 hours. This synthesis time is roughly an order of magnitude lower than that of the process conducted at room temperature. The hydrogen sorption kinetics and capacity of this material are comparable to Mg2Ni synthesized at room temperature.

Jan 1, 2002