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By M. Neises, M. Roeb, C. Sattler, S. Stenger

"A two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split carbon dioxide as well as water molecules by extracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source, a promising method exists to produce synthesis gas from water and CO2. An easy way of operation is gained by the combination of a ceramic substrate as the absorber structure, which can be heated to high temperatures with concentrated solar radiation, and of a metal oxide coating which is capable to carry out the redox reactions. The performance and kinetics of a ferrite based redox material coated on ceramic substrates were investigated in a laboratory set-up. CO2 could be reduced with significant conversions. In addition, several side reactions were observed like the formation of carbon and like the Boudouard reaction.IntroductionThe search for alternative energy carriers and for processes able to reuse carbon dioxide stimulates the research for sustainable routes of alternative fuel production. In the scope of this search thermo-chemical processes combined with sources of concentrated solar energy have become more and more attractive. Ideally, the only raw materials for such processes are water (H2O) and carbon dioxide (CO2) enabling not only a process free of emissions, but also allow to reduce emissions of other processes by reusing CO2 to provide synthesis gas, which itself can be applied to produce chemical commodities or even better synthetic fuels like methanol or petrol.In contrast to the direct splitting of those raw materials, thermochemical cycles split water and CO2 in several steps and enable hydrogen (H2) and carbon monoxide (CO) generation at temperatures controllable by today’s technical equipment. One of the most interesting thermochemical cycles is a two-step process using metal oxide based redox systems. During the first step of this cycle (the regeneration step) the metal oxide is reduced setting some of its lattice oxygen free according to reaction (1). In the next step (the splitting) the reduced and activated material is oxidised by withdrawing oxygen from water and CO2 and at the same time hydrogen and CO is set free according to reactions (2a) and (2b) respectively."

Jan 1, 2011

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 Huimin Lu, Lian Zhou, Qiang Li

"A three-dimensional mathematical model is developed for the regenerative rotary hearth furnace with 40 meters medium diameter. The influence of combustion switchover and outlet pressure on the fluctuation and distribution of temperature and pressure is studied with numerical simulation method. The results showed that the temperature field and flow field is suitable for requirement of industrial production; the fluctuation of the temperature field and pressure is acceptable; the influence of outlet pressure on the furnace pressure is great.IntroduceRotary hearth furnace which is originally utilized as heat treating and reheating industrial furnace, now is also used for carbon based DRl production. With the need of market and the concern of resource recycling and environmental issues, the DRl production from ore or from waste material by rotary hearth furnace attracts more and more attentions from steel industry [1,2].When rotary hearth furnace works, the feed pellets are charged on the hearth and rotate within an annular furnace chamber with the process of reduction. For the sake of rapid reduction, usually the depth of the pellet is one or two layers, accounting for less than 90% of the volume of furnace. As result, the exhaust gases carry away a lot of heat, so that energy utilization efficient is low [3]. Currently, in order to reduce the consumption of energy and improve the production efficiency, many methods have been adopted. The regenerative combustion technology is one of the most promising."

Jan 1, 2013

By J. M. Shneerson

At Gipronickel Institute a technological flowsheet of pressure leaching of copper from rich copper concentrates (i.e. containing: Cu -59-75%; Ni -D.5-4.64%; Fe -D.2-J.3%; S -21.8-26.9%) was developed. As a result, the possibility of deep decomposition of copper-containing minerals with extraction of elemental sulphur (up to 90-95%) was established. The obtained sulphur concentrates contain 80-90% of elemental sulphur, which can be separated from sulphide residue through autoclave melting and settling. As a rule, sulphide concentrates remaining after extraction of sulphur contain up to 1-2% of noble metals. The sulphide concentrate can be purified to the level of rich concentrates or pure metals using the well-known methods as in the case of tankhouse slimes. The presented research specifies the parameters of main operations: pressure leaching and sulphur extraction. It was established that 98% of copper could be transferred into solution at temperatures of 108-1 10°C and oxygen partial pressure 0.4-0.6 MPa. Experiments were carried out in autoclaves of various volumes using the products of nickel matte processing.

Jan 1, 2003

By Rejane Tubino Geyer

The volume of electric arc furnace (EAF) plus oxygen (BOF) slag produced yearly in the world is about 84 million ton. Because of this, the study of recycling processes as a way to solve the storage problem of these slags rise in importance. There are, however, some inconvenients on using this byproduct: lime, which takes part of the process of steel production, remains as a non-reactive raw product in the slag. Since lime reacts in presence of humidity, forming expansive compounds, slag use is strongly limited. There are some utilizations for the electric arc furnace and oxygen slag in the Civil Construction Industry, mainly as base, subbase and asphalt covering in highways. However, independently of the type of recycling, a period of "cure" of about six months is necessary. Because of this slow cure process this byproduct may turn non-competitive in some regions if compared, for example, with the natural aggregate. The objective of this work is to present the flowsheet of the slags production as a residue both at the electric and oxygen steel plants and, through a bibliographic review, to analize the possibilities and limiting factors for the use of steelmaking slags in the Civil Construction Industry.

Jan 1, 1996

Many studies have been conducted over the past 3 decades on the leaching of gold in solutions containing thiosulfate, ammonia and copper. However, most of these studies have been carried out using ore samples, with very few fundamental studies of this system being attempted. The majority of the published studies have failed to acknowledge the undesirable side reaction between copper(H) and thiosulfate, let alone account for its effect. The fact that the solution chemistry is constantly changing makes it very difficult to perform a fundamental study of gold leaching. With the advent of the rotating electrochemical quartz crystal microbalance (REQCM), such fundamental studies are possible as this instrument measures mass in real time. This has allowed leach kinetics to be measured in a matter of minutes and hence at essentially constant solution conditions; The present paper highlights that a sufficient concentration of copper(II) and ammonia are required in order to achieve appreciable gold leach rates. However, the use of air (oxygen) to maintain the copper(Il) concentration catalyses the undesirable copper(II) reaction with thiosulfate. The presence of ammonium ions is shown to have an effect on this undesirable reaction as well as on the gold leaching ?reaction. Preliminary electrochemical studies into .gold electrowinning using the REQCM show that gold(I) thiosulfate cannot be readily reduced to metallic gold in the potential region at which cementation usually occurs. However, it is well known that gold cementation onto copper occurs rapidly. The current study addresses this discrepancy by studying the effect that copper and silver have on the reduction of gold thiosulfate. It has been found that the presence of both silver and copper enhance gold deposition, particularly at low over potentials. While this is beneficial in cementation, the presence of copper and silver in solution has been found to cause passivation of the cathode surface during electrowinning at 'higher overpotentials.

Jan 1, 1998

By T. Maruyama

Tamano Smelter of Hibi Kyodo Smelting Co., Ltd. has been operating with one Flash Furnace (FSFE) and three Peirce-Smith Converters since its start-up in 1972. Anode production capacity has increased from 101,000 to 263,000 t/y by the several expansion programs, while converter capacity has increased and stable operation has been established by several improvements as listed below. - Expanding the furnace body (length) - Development of two kinds of automatic scrap charging system for each converter. (Increasing the in-stack time and better control of the melt temperature) - Oxygen enrichment at slag blow and copper blow - Increasing the blowing rate This paper reports the details of these improvements.

Jan 1, 1998

By David Tisdale, Phillip Mackey, Nagendra Tripathi, Matthew Kreuh, Pascal Coursol

Xstrata Nickel’s Sudbury smelter operation is based on fluid bed roasting of Ni-Cu sulphide concentrate, followed by electric furnace reductive smelting and Peirce-Smith converting to produce a Bessemer matte for electro refining, along with sulphuric acid produced from smelter gas. While the site dates back to the 1930s, the present smelter configuration has been operational since 1978, and currently has a nominal capacity of about 67,000 tpy of contained nickel and is investigating options to expand in future up to 85,000 tpy. As part of a review of plant capacity options, a new metallurgical model of the plant was developed in order to examine a number of processing alternatives. Based on the METSIM™ platform, the present model includes the ability to examine the impact of a number of plant parameters on potential plant performance including; for example, the following: percent of sulphur elimination in roasting, matte grade, degree of matte metallization, temperature, coke requirements, sulphuric acid production, CO2 emissions and overall energy requirements. The process model also includes a number of special features adopted; for example, approaches to effectively model the complex Ni-Cu-Co-Fe-S-O matte system. This paper provides a description of the model and gives an overview of the results. As well as presenting the results of the present study, the applicability of this modeling approach to pyrometallurgical systems in general is also briefly discussed in the paper.

Jan 1, 2009

By Theo Lehner

The Rönnskär smelter has wide experience in the field of recycling of non-ferrous metals. Today, smelting and refining from primary and secondary raw materials are integrated in a complex flow sheet. Boliden operates a lead flash smelter, a lead refinery, a copper smelter and refinery, a sulphuric acid and sulphur dioxide plant, a slag fuming plant and precious metal plant at its Rönnskär smelter in the North of Sweden. The Business Area Smelter Operations also incorporates Boliden Bergsöe, Sweden's lead-acid battery recycler, and Norzink, Norway, where recycled zinc accounts for more than 20% of it's production. Raw materials for the Rönnskär smelter include concentrates, ashes, slags, metallic scrap, electronic scrap and electric arc furnace (EAF) steel-making dust. This paper briefly describes current operations and illustrates current measures to improve productivity. Limits to recycling as experienced by a non-ferrous smelter are, illustrated. The deportment of critical elements contained in raw materials is also discussed.

Jan 1, 1998

By Lloyd R. Nelson

Selective carbothermic reduction is the preferred method of treatment of electric arc furnace (EAF) dust (listed hazardous waste, K061). The process maximizes the recovery of recyclable constituents by concurrent production of saleable zinc metal (directly condensed from the furnace off-gases), an innocuous, disposable iron oxide-rich slag, and some metallic iron. Results of a mineralogical investigation of a foaming slag produced during selective carbothermic reduction treatment of EAF dusts are presented. Wiistite and tricalcium silicate were identified by reflected light microscopy as the primary crystalline phases contained in a glassy matrix, but this technique failed to reveal any solid phases that could have significantly contributed to foam stability. It was concluded therefore, that the foam had been unstable, and had been primarily generated by copious gas evolution associated with the sudden reduction of the slag by an inadvertent addition of carbonaceous reductant. This is consistent with the susceptibility to foaming, when subjected to sudden excesses of carbon, of the slags produced by selective carbothermic reduction, because they still contain unreduced components such as iron oxide.

Jan 1, 1994

By E. J. Peuraniemi

Primary copper production using suspension smelting techniques like Outokumpu Flash Smelting always causes some dust formation. Flue dust particles are formed when sulphide feed material reacts violently with oxygen inducing particle disintegration and total desulphurisation of fragments. In the process, flue dust follows the off-gases to the heat recovery boiler (HRB) where its sulphation takes place because of prevailing conditions. Sulphation releases heat and causes also a drop in particle melting temperature and, further, particle sticking to the walls and heat exchange tube banks. Sulphation of synthetic CU20 particles were examined using a laboratory scale fluid-bed reactor. This study aims to a better understanding of flue dust behaviour in a HRB and, thus, to a better operational practise and design of a HRB. The effect of PSO/PO2 -ratio and temperature on the sulphation kinetics were tested. Standard chemical analysis, light optical and scanning electron microscopy with energy dispersive spectroscopy were used to examine the samples.

Jan 1, 2001

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

By E. Fregeau-Wu

The mineralogy and grain size distribution of phases in a steelmaking slag and experimental products from the heating of the slag under various conditions were determined to explore the possibility of recycling of the iron and manganese to the blast furnace. The steelmaking slags consisted of three major phases: dicalcium silicate, dicalcium ferrite, and Mg-Mn-wustite. Most of the phosphorus was contained in the dicalcium silicate and to lesser extent in the dicalcium ferrite. Due to the fine grain size of the dicalcium silicate, grinding and magnetic separation required pretreatment to increase the grain size and hence the liberation. Experiments on a steelmaking slag were conducted by heating the slag to 1633-1748°K( and slow-cooling in an inert atmosphere at various rates with or without the addition of fluorspar (CaF2) as a flux. Grain size distribution analyses of the starting material and the slow-cooled products were performed using the SEM-IPP area scan method and the QEM*SEM linear scan method. Comparable and reproducible results were obtained on the same sample using both methods. A size versus volume percent plot showed the increased grain growth most effectively. Examples of the grain size distributions obtained were used to show that a higher soaking temperature prior to slow-cooling, a slower cooling rate, and the addition of fluorspar to the slag promoted grain growth.

Jan 1, 1989

By D. M. Hausen

It has been demonstrated that microscopic techniques can be applied in a practical manner to the study of spodumene liberation in the processing of pegmatitic ores at the Kings Mountain spodumene plant, Kings Mountain, North Carolina. Spodumene and associated non-opaque gangue minerals are identified and quantified by microscopic point-counting of polished thin sections of heads, concentrates, middlings and tails fractions. Specially prepared polished thin sections? provide uniform thickness of particles for measurement of diagnostic optical properties and the alternate use of incident and transmitted light in distinguishing the various gangue and ore minerals. Spodumene is commonly associated and interlocked with quartz, albite, microcline and muscovite. Concentrate grade depends on the degree of spodumene liberation, which in turn depends on the crystal size and textural association of interlocked minerals. The liberation of spodumene can be measured as a function of screen size by means of microscopic point-count data. Microscopic data also provide useful metallurgical information about the nature of diluent minerals in spodumene concentrates, and the form of lithia losses in the tails. Lithium assays correlate closely with microscopic spodumene analyses in various flotation products from Foote Mineral's Kings Mountain plant, and confirm the applicability of quantitative optical microscopy to the study of liberation and recovery of spodumene from pegmatitic ores. A better understanding of recovery-grade relationships was developed as a result of quantitative microscopy studies.

Jan 1, 1981

By William Petruk

A fully automatic image analysis system that consists of a microprobe, an energy dispersive x-ray analyzer, and an image analyzer was developed at CANME:I' to determine mineral behaviour that affects beneficiation. The interlacing between the instruments permits automatic identification and characterization of minerals in samples of unbroken ore pieces and of mill products. Different types of information are obtained for minerals in samples of unbroken ore pieces than in samples of mill products, and are used differently. For unbroken ore pieces size distributions are determined for discrete mineral grains to predict a grind at which they might be liberated, and other measurements are Irade to predict the percentage of mineral that occurs as nonrecoverable grains. For mill products the minerals are analysed to determine percentages that (1) are free, (2) are likely to be recovered in concentrates, (3) are likely to be lost to tailings, and (4) could be liberated with regrinding. The image analysis data for mill products are processed by a mineral-metals balance program to determine the distributions of free and unliberated mineral grains at each point in a concentrator, pilot plant or bench test. For samples containing trace minerals, such as gold, an automatic search technique is used to scan the entire area of the polished section for the trace mineral grains. The identified trace mineral grains are characterized with regard to size, liberation, and other properties.

Jan 1, 1988

By KNona C. Liddell

"Many metal recovery processes involve heterogeneous reactions in porous media accompanied by fluid flow and mass transfer. Modeling such systems is difficult because of the number of rate processes involved and is complicated even further by effects due to the structure of the porous medium. Data on even bulk properties of the medium are often severely limited or unavailable. For many such systems, a cell model may provide an attractive alternative to models based on transport mechanisms in a differential volume. A cell model requires less input data and is computationally efficient. Identical residence time distributions can be obtained with models of both types, and both allow conversion and concentration profiles and histories to be calculated. The formulation and properties of cell models for metals recovery are described in detail.INTRODUCTIONSubsurface mineral leaching, metal ion recovery and environmental remediation are significant modeling challenges. They involve one-, two-, or three-dimensional reactive flow in multi reaction open systems. Dissolution, adsorption, and ion exchange occur at reactive mineral surfaces, and these heterogeneous reactions are accompanied by acid-base, complexation, and redox reactions in the solution phase.Two approaches have been taken to reactive flow problems in geologic media: mixing cell and transport models. Mixing cell models, the subject of this review, are based on a network of connected cells, each with a specified number of input and output streams. Mixing cells are assumed to have no internal solute concentration gradients, that is, each cell behaves like a well-stirred tank. Gradients are represented by step changes between connected cells; this results in a model that is spatially discretized at the outset. Different methods of discretizing the model equations are considered more fully below. Although this is not strictly necessary, it has usually been assumed in subsurface flow applications that all cells in the network have the same volume and identical initial properties."

Jan 1, 1996

By John J. Moore

This paper discusses the application of a video technique to construct stability diagrams for the combustion synthesis of ceramic-metal composites. Several model exothermic combustion synthesis reactions have been used to investigate the effect of the reaction parameters, eg. stoichiometry, green density, etc, on the stability of the propagating combustion reaction front and subsequent product morphology. The effect of varying the reactants and their stoichiometry to provide a range of reactant and product species ie. solids, liquids and gases, in the synthesis of both dense and expanded (foamed) ceramic and ceramic-metal composites was also investigated with respect to their corresponding combustion front stabilities.

Jan 1, 1993

By Pavol Loderer

Mineral froth pumping utilising centrifugal slurry pumps is a major engineering challenge for the end users and pump manufacturers due to the undesirable outcome of unstable pump performance. Most of these challenges occur due to incorrect pump selection and suction tank design. The traditional approach is to oversize the pump for pumping mineral froth. New horizontal slurry froth pump designs offer opportunities to improve the mineral froth with challenging (high) Froth Volume Factor while maintaining high efficiency, long wear life and stable pumping performance. This paper examines the flotation process in detail and how froth pumps are designed to handle this arduous process.

By E. C. L. Cardoso

Hydrocarbon polymers, as PP, made from cheap petrochemical feedstock are important in many branches of industry. However, they have an undesirable influence on the environment and cause problems due to waste deposition and utilization. Polymeric materials composites account for an estimated from 20 to 30% of total volume of solid waste disposed. Thus, there is a tendency to substitute such polymers by those ones that undergo biodegradable processes. Polypropylene (PP) is a commodity, with high melting point, high chemical resistance, low density, with a balance between physical and mechanical properties and easy processing at low cost. Nevertheless, PP shows limitations for some special applications in automotive industry and civil construction. In order to minimize this deficiency, related to rheological behavior of polymer melt, especially referring to viscosity in processing temperature, a 50% mixture with HMSPP (High melt Strength Polypropylene) was used. PP/HMSPP was blended with 10, 15, 30 and 50% of natural (sugarcane bagasse) and synthetic polymers (PHB and PLA) aiming to partially biodegradable materials. The admixtures were subjected to gamma-irradiation at 50, 100, 150 and 200 kGy and then further assessed by mechanical tests in order to evaluate their degradability.

Jan 1, 2015

By Alexandra Anderson

A computational fluid dynamic (CFD) model has been developed using ANSYS Fluent 17.0 to help identify areas of high wear within the refractory lining of a secondary lead reverberatory furnace. Once a base case simulation was validated using data from an operational furnace, areas of potentially high refractory wear were determined through the calculation of the temperature and velocity distributions within the furnace and on the hot face of the refractory lining. The CFD model was used to assess whether the predicted areas of high refractory wear could be minimized through changes burden geometry. The results showed that shape of the burden geometry greatly affected the overall flow patterns and heat transfer within the furnace.