Made available in DSpace on 2014-06-11T19:30:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-11-05Bitstream added on 2014-06-13T19:18:32Z : No. of bitstreams: 1 magalhaes_lc_me_guara.pdf: 2627349 bytes, checksum: 8fadf3c86720e6a184e9fb846efb6c45 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Esta dissertação analisou a viabilidade técnica de gaseificação de lama de alto de alto forno da ArcelorMittal Tubarão para produção de gás visando uma utilização interna. A gaseificação foi conduzida através de simulação em modelo de equilíbrio químico TCW - Termochemical Information and Equlibrium Calculation. Foram simuladas 3 misturas para gaseificação: a) 100% carvão metalúrgico de alto volátil (base das misturas), b) de lama de alto forno com 85% de carvão metalúrgico alto volátil e c) de lama de alto forno com 75% de carvão metalúrgico alto volátil. Os dois parâmetros principais que definiram a viabilidade técnica de gaseificação de lama de alto forno foram poder calorífico inferior - PCI e faixas de trabalho temperaturas no reator. O PCI do gás foi calculado a partir das frações molares de H2 e CO contidas no gás obtidos nas misturas simuladas / This dissertation analyzed the technical viability of blast furnace slurry gasification with the objective of using the obtained gas at ArcelorMittal Tubarão. The process was simulated using an equilibrium program, the TCW - Termochemical Information and Equilibrium Calculation. Three mixtures were considered for gasification: a) 100% high volatile metallurgical coal (the base of the mixtures), b) 15% slurry and 85% coal, and c) 25% slurry and 25% coal. The two main parameters that defined the technical viability of the blast furnace slurry were the mixture Low Heat Value (LHV) and the temperature ranges for work in the gasification reactor. The LHV was calculated from the molar fractions of H2 and CO in the gas obtained in the simulation

Made available in DSpace on 2014-06-11T19:30:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-06-23Bitstream added on 2014-06-13T20:00:02Z : No. of bitstreams: 1 silva_am_me_guara.pdf: 2611520 bytes, checksum: 4ed9180c920917190d4d02d7ae6dd990 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho apresenta um estudo da queima de material combustível sólido injetado nas ventaneiras de um alto forno. O estudo é baseado na queima de carvões minerais e misturas considerando as reações de combustão, os parâmetros da qualidade do carvão (teor em material volátil, cinzas, carbono e oxigênio) e a análise micro-estrutural dos resíduos gerados após a queima no simulador de combustão, montado no centro de pesquisas da Companhia Siderurgica Nacional. Foi avaliada a taxa de reação do carbono dos carvões e misturas queimadas em uma termo balança. Ficou confirmado no estudo que a taxa de substituição do coque metalúrgico pelo carvão queimado no alto forno é influenciada pela eficiência de queima e que, por sua vez, é significativamente dependente das suas propriedades e das condições operacionais do alto forno. Através dos resultados obtidos ficou comprovado que os carvões com alto teor em matéria volátil queimam com maior eficiência quando comparados com os carvões de médio e baixo voláteis, porém devido ao menor teor em carbono, a sua taxa de substituição foi menor quando comparada com os carvões baixo e médio voláteis. Os carvões com maior eficiência de queima e reatividade apresentaram menor taxa de substituição nos altos fornos, quando comparados com as misturas. A análise micro-estrutural realizada nos carvões e misturas confirmou a maior eficiência de queima nos carvões mais reativos. Quanto ao coque verde de petróleo, este se mostrou de baixa eficiência de queima; porém, quando misturado a carvões de elevada reatividade, o mesmo apresentou uma eficiência de queima significativamente maior. Os resultados tanto de qualidade de ferro gusa quanto da redução de consumo de combustível nos altos fornos foram satisfatórios quando se injetou a mistura com 50% de participação. / This work presents a study on combustion of solid fuel injected in blast furnace tuyeres. The study is based on the combustion of mineral coals and blends considering the combustion reactions, the coal quality parameters (volatile matter, ash, carbon and oxygen content) and the micro structural analysis of the residues generated after coals and blends be burned it in the simulator, set up in the National Steel Company research center. The reaction rates of carbon for the coals and blends burned in a thermo balance were evaluated. It was confirmed in the study that the rate of coke replacement for the coal burned in the blast furnace is strongly influenced by the combustion efficiency, which is significantly dependent on properties and on operational conditions of the furnace. It was proven, with the obtained results, that the high volatile coals burn with higher efficiency when compared to medium and low volatile coals, but due to the lower carbon content, its replacement rate was lower when compared with low and medium volatile coals. The coals with larger combustion efficiency and reactivity presented lower replacement rates in the blast furnace, when compared with the coal blend. Micro structural analysis conducted in the coals and blends confirmed higher combustion efficiencies in more reactive coals. In relation to the green petroleum coke, it presented low combustion efficiences. However, when mixed with high volatile and high reactivity coals, its combustion efficiency was significantly increased. The results relative to the quality of the hot metal and to the reduction of fuel consumption in the blast furnace, when the blend had injected with 50% of the petroleum coke, were satisfactory.

Abstract A procedure is defined for commercializing slags arising as by-products of steelmaking, and this is used to develop certain products. The outcome of the present work comprised three products or groups of products: 1) slag-based binding agents, 2) a road structure improved by means of stabilization with such binding agents, and 3) a procedure for designing stabilized structures. The commercialization procedure was drawn up by examining the technical properties of the initial materials, excluding environmental acceptability and the mechanisms of their chemical reactions. The research proceeded in stages, of which the first was a reconsideration of the results presented in the author's licentiate thesis concerning factors affecting the stabilization of road construction aggregates with blast-furnace slag-based binding agents and their significance. This was followed by a series of experiments designed to test the validity of these results. At the third stage the selection of slag-based binding agents was extended to include LD steel slag products, while the final stage consisted of the implementation of a set of test structures and associated preliminary experiments and monitoring measurements. The binding properties of three blast-furnace slag products and three LD steel slag products, used separately or in various combinations, were examined in the course of this work, taking cement as a reference material. Materials were then eliminated as the research proceeded, either on account of their poor binding properties or on economic grounds. The final construction experiments were performed with three combinations: cement-activated granulated blast-furnace slag, LD steel slag-activated granulated blast-furnace slag and a mixture of ground granulated blast-furnace slag and cement. The actual novel product among the slag-based binding agents to be introduced here is LD steel slag-activated granulated blast-furnace slag, which was found to be similar in its technical properties to cement-activated granulated blast-furnace slag. Structural layers stabilized with these two binding agents showed very similar bearing capacities, although the former did not reach the same compression strengths at an age of 91 days. The reasons for these similarities lay in a larger amount of binding agent used when activated with LD steel slag and the greater thickness of the stabilized layer, factors which both tended to compensate for the poorer compression strength. The new information gained on the properties of cement-activated granulated blast-furnace slag and the mixture of ground granulated blast-furnace slag and cement opens up fresh opportunities for selecting binding agents and designing road structures. Formulae were developed here for predicting the uniaxial compression strength at 91 days, used as a stabilization criterion, from the value for a sample taken at 28 days, a technique which will speed up the assessment of stabilization results, especially when using slowly reacting slag-based binding agents.

Fly ash and blast furnace slag are the two major industrial solid by-products generated in most countries including India. Although their utilization rate has increased in the recent years, still huge quantities of these material remain unused and are stored or disposed of consuming large land area involving huge costs apart from causing environmental problems. Environmentally safe disposal of Fly ash is much more troublesome because of its ever increasing quantity and its nature compared to blast furnace slag. Bulk utilization of these materials which is essentially possible in civil engineering in general and more particular in geotechnical engineering can provide a relief to environmental problems apart from having economic benefit. One of the important aspects of these waste materials is that they improve physical and mechanical properties with time and can be enhanced to a significant level by activating with chemical additives like lime and cement. Class-C Fly ashes which have sufficient lime are well utilized but class-F Fly ashes account for a considerable portion that is disposed of due to their low chemical reactivity. Blast furnace slag in granulated form is used as a replacement for sand to conserve the fast declining natural source. The granulated blast furnace slag (GBS) is further ground to enhance its pozzolanic nature. If GBS is activated by chemical means rather than grinding, it can provide a good economical option and enhance its utilization potential as well. GGBS is latent hydraulic cement and is mostly utilized in cement and concrete industries. Most uses of these materials are due to their pozzolanic reactivity. Though Fly ash and GGBS are pozzolanic materials, there is a considerable difference in their chemical composition. For optimal pozzolanic reactivity, sufficient lime and silica should be available in desired proportions. Generally, Fly ash has higher silica (SiO2) content whereas GGBS is rich in lime (CaO) content. Combining these two industrial wastes in the right proportion may be more beneficial compared to using them individually. The main objective of the thesis has been to evaluate the suitability of the class-F Fly ash/GGBS mixtures with as high Fly ash contents for Geotechnical and Geo-environmental applications. For this purpose, sufficient amount of class-F Fly ash and GGBS were collected and their mixtures were tested in the laboratory for analyzing their mechanical behavior. The experimental program included the evaluation of mechanical properties such as compaction, strength, compressibility of the Fly ash/GGBS mixtures at different proportions with GGBS content varying from 10 to 40 percent. An external agent such as chemical additives like lime or cement is required to accelerate the hydration and pozzolanic reactions in both these materials. Hence, addition of varying percentages of lime is also considered. However, these studies are not extended to chemically activate GBS and only GGBS is used in the present study. Unconfined compressive strength tests have been carried out on various Fly ash/ GGBS mixtures at different proportions at different curing periods. The test results demonstrated rise in strength with increase in GGBS content and with 30 and 40 percent of GGBS addition, the mixture showed higher strength than either of the components i.e. Fly ash or GGBS after sufficient curing periods. Addition of small amount of lime increased the strength tremendously which indicated the occurrence of stronger cementitious reactions in the Fly ash/GGBS mixtures than in samples containing only Fly ash. Improvement of the strength of the Fly ash/GGBS mixtures was explained through micro-structural and mineralogical studies. The microstructure and mineralogical studies of the original and the stabilized samples were investigated by scanning electron microscopy (SEM) and X-Ray diffraction techniques respectively. These studies together showed the formation of cementitious compounds such as C-S-H, responsible for imparting strength to the pozzolanic materials, is better in the mixture containing 30 and 40 percent of GGBS content than in individual components. Resilient and permanent deformation behavior on an optimized mix sample of Fly ash and GGBS cured for 7 day curing period has been studied. The Resilient Modulus (Mr) is a measure of subgrade material stiffness and is actually an estimate of its modulus of elasticity (E). The permanent deformation behavior is also important in predicting the performance of the pavements particularly in thin pavements encountered mainly in rural and low volume roads. The higher resilient modulus values indicated its suitability for use as subgrade or sub-base materials in pavement construction. Permanent axial strain was found to increase with the number of load cycles and accumulation of plastic strain in the sample reduced with the increase in confining pressure. Consolidation tests were carried on Fly ash/GGBS mixtures using conventional oedometer to assess their volume stability. However, such materials develop increased strength with time and conventional rate of 24 hour as duration of load increment which requires considerable time to complete the test is not suitable to assess their volume change behavior in initial stages. An attempt was thus made to reduce the duration of load increment so as to reflect the true compressibility characteristics of the material as close as possible. By comparing the compressibility behavior of Fly ash and GGBS between conventional 24 hour and 30 minutes duration of load increment, it was found that 30 minutes was sufficient to assess the compressibility characteristics due to the higher rate of consolidation. The results indicated the compressibility of the Fly ash/GGBS mixtures slightly decreases initially but increase with increase in GGBS content. Addition of lime did not have any significant effect on the compressibility characteristics since the pozzolanic reaction, which is a time dependent process and as such could not influence due to very low duration of loading. Results were also represented in terms of constrained modulus which is a most commonly used parameter for the determination of settlement under one dimensional compression tests. It was found that tangent constrained modulus showed higher values only at higher amounts of GGBS. It was also concluded that settlement analysis can also be done by taking into account the constrained modulus. The low values of compression and recompression indices suggested that settlements on the embankments and fills (and the structures built upon these) will be immediate and minimal when these mixtures are used. In addition to geotechnical applications of Fly ash/GGBS mixture, their use for the removal of heavy metals for contaminated soils was also explored. Batch equilibrium tests at different pH and time intervals were conducted with Fly ash and Fly ash/GGBS mixture at a proportion of 70:30 by weight as adsorbents to adsorb lead ions. It was found that though uptake of lead by Fly ash itself was high, it increased further in the presence of GGBS. Also, the removal of lead ions increased with increase in pH of the solution but decreases at very high pH. The retention of lead ions by sorbents at higher pH was due to its precipitation as hydroxide. Results of the adsorption kinetics showed that the reaction involving removal of lead by both the adsorbents follow second-order kinetics. One of the major problems which geotechnical engineers often face is construction of foundations on expansive soils. Though stabilization of expansive soils with lime or cement is well established, the use of by-product materials such as Fly ash and blast furnace slag to achieve economy and reduce the disposal problem needs to be explored. To stabilize the soil, binder comprising of Fly ash and GGBS in the ratio of 70:30 was used. Different percentages of binder with respect to the soil were incorporated to the expansive soil and changes in the physical and engineering properties of the soil were examined. Small addition of lime was also considered to enhance the pozzolanic reactions by increasing the pH. It was found that liquid limit, plasticity index, swell potential and swell pressure of the expansive soil decreased considerably while the strength increased with the addition of binder. The effect was more pronounced with the addition of lime. Swell potential and swell pressure reduced significantly in the presence of lime. Based on the results, it can be concluded that the expansive soils can be successfully stabilized with the Fly ash-GGBS based binder with small addition of lime. This is also more advantageous in terms of lime requirement which is typically high when Fly ash, class-F in particular, is used alone to stabilize expansive soils. Based on the studies carried out in the present work, it is established that combination of Fly ash and GGBS can be advantageous as compared to using them separately for various geotechnical applications such as for construction of embankments/fills, stabilization of expansive soils etc. with very small amount of lime. Further, these mixtures have better potential for geo-environmental applications such as decontamination of soil. However, it is still a challenge to activate GBS without grinding.

Résumé : L’auto-cicatrisation des fissures des matériaux cimentaires présente un intérêt important pour améliorer leur durabilité (propriétés de transfert par exemple). L’impact du laitier de haut-fourneau sur ce phénomène a été peu étudié bien qu’il ait été observé sur des ouvrages du Génie Civil. Dans cette étude, la cinétique et l’amplitude de l’auto-cicatrisation ont été suivies par des essais non destructifs : la tomographie aux rayons X et la perméabilité à l’air, pour une fissuration créée à 7 jours et à 28 jours. Les résultats montrent que le laitier de haut-fourneau possède un potentiel d’auto-cicatrisation intéressant pouvant dépasser les résultats obtenus pour les formulations de référence sans laitier. Ce bon potentiel dépend des caractéristiques physico-chimiques des matériaux brutes et du potentiel d’hydratation de la formulation au cours du temps. De plus pour suivre l’auto-cicatrisation, un nouvel essai a été mis en place afin de fissurer les éprouvettes de mortier par retrait gêné et d’étudier l’auto-cicatrisation d’une fissure naturelle. Cet essai s’est avéré efficace sur la formulation de référence. Une caractérisation des produits de cicatrisation par MEB-EDS témoigne de la formation de nouveaux produits dans les fissures et de l’impact important des conditions de stockage sur le type de produits formés: des C-S-H pour un stockage sous eau et des carbonates de calcium pour un stockage en chambre humide (CO2 + eau). Les résultats de migration aux chlorures de nano-indentation montrent que ces produits de cicatrisation possèdent de bonnes propriétés de durabilité et des propriétés mécaniques à l’échelle microscopique intéressantes (pour le carbonate de calcium). Enfin, une modélisation du phénomène d’auto-cicatrisation est proposée au moyen du code de calcul de géochimie PHREEQC. L’étude a révélé le potentiel intéressant de PHREEQC pour modéliser l’auto-cicatrisation et en faire un outil de prédiction du phénomène. / Abstract : Self-healing of cementitious materials presents great interest to improve the durability of concrete structure (transfer properties for example). The impact of blast-furnace slag on this phenomenon is not yet clear even if the self-healing of concrete with blast-furnace slag was observed in building sites. To understand the blast-furnace slag influence, non-destructive methods were used to follow self-healing: X-ray tomography and gas permeability test. All specimens were cracked at 7 days and 28 days. The results show that the blast furnace slag has an interesting self-healing potential that can exceed the reference formulation results. This good potential depends on the physico-chemical characteristics of the raw materials and the hydration potential of the formulation over time. In addition to follow the self-healing, a new trial was set up to crack mortar specimens by restrained shrinkage and study the self-healing of a natural crack. In addition to follow the self-healing, a new trial was set up to crack mortar specimens by restrained shrinkage and study the self-healing of a natural crack. This test has proven effective over the reference formulation.The SEM with EDS analysis showed the formation of new products in the crack and the impact of storage conditions on these products : C-S-H for specimens stored in water and calcium carbonate for specimens stored in a damp chamber (CO2 + water). Migration chlorures and nano-indentation tests results showed that self-healing products had interesting durability properties and micro-mechanical properties (for calcium carbonate). Finally, self-healing modelling is proposed by means of geochemistry PHREEQC calculation code. The study revealed interesting potential PHREEQC to model self- healing phenomenon and make it a of predictive tool.

<p>Four different kinds of filter-materials with reactive surfaces have been studied concerning their capacity to absorb heavy metals in leachate from a municipal waste deposit. The heavy metals studied were: lead, cadmium, copper, mercury, chromium, nickel and zinc. The leachate contains high levels of dissolved organic carbon (DOC) and has a high pH-value along with a high buffer capacity. These characteristics of the leachate make it difficult to remove pollutants and require efficient filters. The filters that were examined in the report are blast-furnace slag with CaO, sand covered with iron oxides, olivine and nepheline. The experiment was carried out in two sets, starting with batch experiments followed by a column study. The objective of the batch experiments was to find out how variations in pH affected the sorption capacity of the materials. The interval used during the test was from pH 5 to pH 10. The computer program VisualMinteq was used to evaluate the dominating sorption processes when the materials interacted with the solutions. Two different kinds of solutions were used in the batch experiment. One of them was the leachate, to which known concentrations of heavy metals were added (about 1 μM) and the other consisted of sodium nitrate, a solution without organic compounds, which was used as a reference. The sodium nitrate solution was also spiked with the same concentration of heavy metals as the leachate.</p><p>The results from the batch experiment showed that the sorption of heavy metals was lowered if the DOC level was high. No relation between pH and sorption ability could be found for the leachate, but for some metals in the sodium solution a higher pH improved the removal of heavy metals. The two materials that showed best results in the batch experiment were the blast-furnace slag and the sand with iron oxides. These materials were used in the column study. The olivine material was somewhat better than the nepheline in the batch experiment.</p><p>Four columns were used in the column study, two for each material. Leachate with heavy metals was pumped into the columns with a specific flow rate; at first a low flow rate was used and when half the experiment time had passed the flow rate was increased. The flow rates used were 0.12 m/24 h and 0.62 m/24 h. The outcome of the column experiment showed that the slag had the highest ability to adsorb metals. The metal sorption was over 60 percent for lead, cadmium and zinc, where the highest sorption was obtained for lead. No affects were noticed when the flow rate was increased.</p> / <p>I detta examensarbete har fyra olika reaktiva filtermaterials kapaciteter att ur deponilakvatten avskilja tungmetallerna bly, kadmium, koppar, kvicksilver, krom, nickel och zink testats. Deponilakvatten är ett avloppsvatten med höga halter organiskt material (DOC), högt pH och en hög buffertkapacitet. Dess sammansättning ställer stora krav på ett filter och närvaron av ligander påverkar sorptionprocesserna. Filtren som ingått i studien är kalciumoxiddopad masugnsslagg, järnoxidtäckt sand, olivin och nefelin.</p><p>Försöken utfördes i två delar, med inledande skakförsök och därefter kolonnförsök. I båda försöken användes lakvatten med en extra tillsats av tungmetaller. I skakförsöken användes även natriumnitrat; ett referensvatten utan organiska ligander, även det spikat med tungmetaller. I skakförsöken studerades avskiljningens pH-beroende för de olika filtren, med ett pH-intervall på ca 5 – 10. Därefter modellerades resultaten i jämviktsprogrammet VisualMinteq för att fastställa vilka processer som styr avskiljningen. Skakförsöken och kolonnförsöken utfördes båda i klimatrum vid 8 ºC, för att efterlikna markens naturliga temperatur.</p><p>Resultaten från skakförsöken visade att masugnsslagg och järnoxidsand gav bäst avskiljning för de flesta tungmetaller. Olivin och nefelin var sämre metallsorbenter, där olivin uppvisade något bättre resultat än nefelin. Inget tydligt pH-beroende för lakvattnet kunde utläsas, men för natriumnitratlösningen gav en pH-höjning en ökad sorption för vissa metaller. Den kemiska jämviktsmodelleringen visade att den dominerande processen i filtermaterialen var sorption på filterytorna. De två filtermaterialen som visade bäst resultat i skakförsöken (slagg och järnoxid) studerades vidare i kolonnförsök, där ett bestämt lakvattenflöde pumpades genom kolonner packade med materialen. Två olika flödeshastigheter testades (0,12 m/dygn och 0,62 m/dygn) och sorptionen av metaller analyserades. Slaggen uppvisade högst avskiljningskapacitet av de studerade filtren. De metaller som sorberades bäst var bly, kadmium och zink (över 60 % avskiljning), där den högsta sorptionen erhölls för bly. Gemensamt för både skak- och kolonnförsöken var att sorptionen försvårades då halten organiskt material (DOC) ökade, vilket beror på att DOC konkurrerar med de reaktiva ytorna på filtren om att binda den fria metalljonen. Ingen minskande avskiljningseffekt av en flödesökning kunde utläsas.</p>

<p>An excessive input of nutrients to lakes and other water bodies has created a problem with eutrophication in Sweden. Untreated, or partially treated, domestic sewage is a major source for discharge of phosphorus (P), which is the nutrient most frequently responsible for eutrophication of most fresh waters and the Baltic Sea. The waste water can be cleaned by filter materials, which have a high P-retention ability and which after saturation may be used as fertilizers. Four potentially suitable filter materials were tested in batch- and column experiments in this study. In the batch experiments, the following materials were shaken with waste water in time series ranging from 5 seconds to 60 minutes: coarse (1-4 mm) and fine (0-2 mm) Polonite® (heated bedrock from Poland); Filtralite® (light expanded clay aggregates with limestone added before burning); water cooled blast furnace slag (BF-slag) and BF-slag mixed with 10% burned limestone. In the column experiment, the phosphorus sorption capacity in BF-slag and BF-slag mixed with burned limestone was observed under saturated and unsaturated flow conditions for 10 weeks. The waste water used in both experiments originated from the full scale testing site at Ångersjön in Sweden. After the column experiment was ended, the filter materials were investigated with XRD (X-ray diffraction) and SEM (scanning electron microscope) in order to figure out which chemical reactions that had taken place.</p><p>The results from the batch experiments show that fine Polonite® and BF-slag mixed with limestone have the fastest P sorption capacity. Already after 5 seconds of shaking the materials showed effective retention of P. The coarse Polonite®, Filtralite® and BF-slag showed similar sorption capacities, although the coarse Polonite® tended to be somewhat inferior. The column studies showed that the materials used in the columns had a sorption capacity of 98 % or more. The XRD and SEM indicated that an amorphous calcium-P-compound was created in the filter material.</p> / <p>I Sverige är reningen av fosfor i vatten från enskilda avlopp ofta bristfällig, vilket bland annat kan leda till övergödning av sjöar, hav och vattendrag. Sedan några år tillbaka har olika filtermaterial med speciella reaktiva egenskaper, som bland annat avskiljer fosfor från avloppsvatten, undersökts. Tanken med filtermaterialen är att de efter mättnad med näringsämnen ska kunnas användas som jordförbättringsmedel. I denna rapport har några olika filtermaterial, lämpade för fosforavskiljning, undersökts genom skak- och kolonnförsök. I skakförsök, där skaktiderna varierade mellan 5 sekunder och 60 minuter, testades Polonite®, Filtralite®, Hyttsand och Hyttsand blandad med 10 % bränd kalk. Polonite® är en upphettad form av bergarten opoka varav två olika kornstorleksfraktioner (0-2 mm och 1-4 mm) användes. Filtralite® och Hyttsand är antropogena filtermaterial. Filtralite® tillverkas i Norge och består av kalkhaltiga kulor av expanderad lera (Leca®). Hyttsand framställs genom vattenkylning av masugnsslagg som bildas vid framställningen av råjärn vid stålverket i Oxelösund. I kolonnförsöken, som utfördes under 10 veckor, studerades Hyttsand och Hyttsand blandad med 10 % bränd kalk under omättade och mättade flödesförhållanden. I samtliga experiment användes avloppsvatten från reningsverket vid Ångersjön, där Filtralite® och Hyttsand testas i fullskala. Efter kolonnförsöken avslutats undersöktes filtermaterialen med XRD (röntgendiffraktion) och SEM (svepelektron mikroskop) för att utreda vilka mekanismer som medverkat vid avskiljningen av fosfor.</p><p>Resultaten från skakförsöken visade att finkornig Polonite® och Hyttsand blandad med kalk avskiljer fosfor effektivt redan efter skakning i 5 sekunder. Grovkornig Polonite, ren Hyttsand och Filtralite® sorberade fosfor tämligen likartat, även om den grovkorniga Poloniten® tenderade att vara aningen sämre än de övriga. Resultaten från kolonnförsöken visade att fosfor kunde avskiljas till över 98 % i alla kolonner och att det bildats amorfa fosfatföreningar, främst med kalcium, under den 2,5 månader långa experimentperioden.</p>

Os finos de resíduos cimentícios (previamente hidratados) podem ser reciclados através de tratamento térmico, tornando-se um ligante alternativo. Quando tratados termicamente em temperaturas inferiores a 550ºC, o processo não gera emissões de CO2 relativas à descarbonatação do calcário. Esta pesquisa teve como objetivo reativar o cimento Portland de alto forno (CP III) previamente hidratado, desidratando-o em temperatura de 500°C com patamar de 2h e reidratando-o com teores de água e de dispersante variados. Inicialmente foram realizadas caracterizações a fim de comparar as características físico-químicas do cimento desidratado com o cimento anidro. Posteriormente, foram analisadas as transformações de fases observadas com a hidratação, desidratação e reidratação do cimento. A segunda parte do estudo foi de otimização das pastas reidratadas e hidratadas, onde foram definidas condições ideais de dispersão, com a saturação ideal de dispersantes e teores mínimos de água resultado em pastas com volume de poros menores e consequentemente resistências mais elevadas. Os resultados obtidos comprovaram que o cimento desidratado se reidrata e forma fases similares às fases formadas na hidratação, como C-S-H, portlandita, hidrotalcita, etc. O cimento de alto forno carbonata mais do que o cimento Portland (CP V). Devido à área superficial elevada (14 vezes superior ao do cimento anidro), o cimento desidratado libera calor de molhagem elevado, consequencia da recombinação da água com as fases desidratadas. Observou-se ainda que, é possível controlar a resistência à compressão da pasta reidratada, otimizando o volume de poros presentes nas pastas. As resistências das pastas reidratadas com dispersante aos 28 dias foram 2,37 vezes maiores quando comparados com sistemas aglomerados. Com relação a porosidade, há indícios que é possível obter níveis de porosidade para as pastas reidratadas semelhantes com a pasta hidratada. / The fines of cementitious wastes (previously hydrated) can be recycled through heat treatment, becoming an alternative binder. When heat treated at temperatures below 550°C, the process does not generate CO2 emissions relative to limestone decarbonation. The objective of this research was to reactivate the previously hydrated Portland cement (CP III), dehydrating it at a temperature of 500°C with a 2-hours plateau and rehydrating it with varying water and dispersant contents. Characterization was initially performed to compare the physicochemical characteristics of dehydrated cement (DC) with anhydrous cement (AC). Subsequently, the AC-HP phase transformations for DC-RP were analyzed. The second part of the study was the optimization of rehydrated (RP) and hydrated (HP) pastes, where ideal dispersion conditions were defined, with optimum dispersant and water minimum contents, resulting in pastes with smaller pore volumes and consequently more compressive strength high. The results confirm that the DC rehydrates and forms phases similar to the phases formed in the hydration, such as C-S-H, portlandite, hydrotalcite, etc. The blast furnace cement carbonate more than Portland cement (no additions). Due to the high surface area (14 times higher than that of the AC), the DC releases high wetting heat, due to the recombination of the water with the dehydrated phases. It was also observed that it is possible to control the compressive strength of the rehydrated paste by optimizing the pore volume present in the pastes. The strengths of dispersed pastes with additives at 28 days were 2.37 times higher when compared to agglomerated systems. With respect to porosity, there are indications that it is possible to obtain porosity levels for the similar rehydrated pastes with the hydrated paste.

A injeção de carvão pulverizado na região das ventaneiras dos altos-fornos (Pulverized Coal Injection – PCI) é uma tecnologia amplamente praticada em altos-fornos com o objetivo de substituir parte do coque empregado por carvões não-coqueificáveis. O carvão injetado fornece energia e gases redutores para o processo de fabricação do gusa, além de contribuir para a redução da emissão de gases poluentes devido à menor produção de coque. Atualmente todo o carvão injetado em altos-fornos brasileiros é importado. O país possui grandes reservas de carvão, porém este carvão necessita passar por processos de beneficiamento para redução dos teores de matéria mineral e enxofre. A flexibilidade do processo PCI permite a utilização de ampla gama de carvões não-coqueificáveis, o que abre a possibilidade para utilização de carvão brasileiro. Este trabalho teve por objetivo avaliar propriedades de carvão brasileiro beneficiado com teor de cinzas de 18,9% para injeção em altos-fornos. O estudo foi conduzido através de ensaios de combustão empregando um moderno simulador de PCI projetado e desenvolvido pelo Laboratório de Siderurgia da Universidade Federal do Rio Grande do Sul (LaSid) e também uma termobalança de modo a ser possível traçar um comparativo entre ambos os equipamentos. Além do carvão brasileiro, de baixo rank, foram utilizados dois carvões importados já em uso para injeção, um de alto e um de baixo rank. A combustibilidade (ou eficiência de combustão) em simulador de PCI foi avaliada pela conversão (burnout), calculada pelo método ash tracer, um balanço de massa entre a quantidade de cinzas que entra e sai do reator. Em termobalança o parâmetro adotado foi a temperatura de pico, correspondente à taxa máxima de reação. Fez-se também a avaliação da reatividade ao CO2 dos chars gerados em simulador de PCI, visto que o char ao deixar a zona de combustão passa por uma zona rica neste gás. Análise estatística revelou que a técnica adotada de burnout mostrou-se bastante eficiente para diferenciar carvões de teores de matéria volátil distintos, porém não no caso de carvões com teores de matéria volátil similares. No simulador de PCI a influência da matéria volátil do carvão foi mais pronunciada do que o rank e em termobalança o rank teve mais efeito sobre a combustibilidade do que a matéria volátil. O carvão brasileiro apresentou propriedades comparáveis às do carvão importado de baixo rank utilizado para PCI. Isto representa uma grande vantagem, visto que possibilitaria a utilização do mesmo na siderurgia. / Pulverized coal injection through blast furnace tuyeres (PCI) is a widely practiced technology in blast furnaces to replace part of coke by non-coking coal. Injected coal provides energy and reducing gases for pig iron production process, as well as contributes to reducing pollutants gases emission due to coke saving. Currently all coal injected into Brazilian blast furnaces is imported. The country has large reserves of coal, but this coal needs to undergo beneficiation to reduce mineral matter and sulfur contents. PCI process flexibility allows the employment of a wide range of non-coking coals, which opens the possibility to use Brazilian coal. This work aimed to evaluate properties of Brazilian coal benefited with 18.9% ash content for injection into blast furnaces. The study was conducted through combustion tests employing a modern PCI test rig designed and developed by the Iron and Steelmaking Laboratory (LaSid) of the Federal University of Rio Grande do Sul (UFRGS) and also a thermobalance in order to draw a comparison between both equipments. In addition to low rank Brazilian coal, two imported coals which are already used for injection were used, one high and one low rank. The combustibility (or combustion efficiency) in a PCI test rig was evaluated by burnout, calculated by the ash tracer method, a mass balance between the amount of ash that enters and leaves the reactor. Peak temperature was the parameter adopted to evaluate combustibility in thermobalance, corresponding to the maximum rate of reaction. It was also evaluated the CO2 reactivity of chars generated in the PCI test rig, since char leaving the combustion zone passes through a CO2 rich area. Statistical analysis revealed that burnout technique proved to be efficient enough to differentiate coals with different volatile matter contents, but not in the case of coals with similar volatile matter contents. In PCI test rig the influence of volatile matter was more pronunced than rank and in thermobalance rank had more effect on combustibility than volatile matter. Brazilian coal showed properties comparable to the ones of imported low rank coal already in use for PCI. This is a great advantage, since it would make it possible to use it in ironmaking.

A injeção de carvão pulverizado (pulverized coal injection - PCI) é uma técnica largamente utilizada nos altos-fornos pelas siderúrgicas brasileiras, seguindo uma tendência mundial, que busca reduzir o consumo específico de coque por tonelada de gusa e, em consequência, do custo do ferro gusa produzido. A combustão do carvão pulverizado ocorre sob pressões médias (de até 4 atm), temperaturas de chama elevadas (em torno de 2 000 °C), altas taxas de aquecimento (104 a 105 °C/s), tempo de residência muito curtos (inferiores a 40 ms), e é seguida pela gaseificação na presença de CO2. Como não existem métodos padronizados para a avaliação das características de combustão dos carvões para sua utilização em PCI, utilizam-se geralmente equipamentos de injeção de carvão em escalas laboratorial e de bancada, além plantas-piloto com este propósito. O objetivo principal deste trabalho é apresentar as etapas do desenvolvimento de um equipamento em escala de bancada realizado no Laboratório de Siderurgia da Escola de Engenharia da UFRGS (LASID-UFRGS), desde o projeto conceitual até a fase pré-operacional, e os resultados iniciais obtidos, para estudar as características de combustão dos carvões em condições bastante similares às que ocorrem nos altos-fornos. Os testes iniciais incluem a avaliação da combustão de um carvão brasileiro objetivando seu uso potencial em PCI, em substituição parcial de carvões importados para este fim. Optou-se por um projeto moderno, altamente automatizado, que inclui aquisição rápida de dados, com escala e conceito operacional adequados para estudos acadêmicos, de configuração vertical e que possibilitasse a operação no modo de injeção de uma amostra de carvão em pulso único, bem como uma adequação futura ao modo de injeção contínua de carvão. Algumas características relevantes do equipamento são a medição e aquisição ultrarrápida de dados termodinâmicos de pressão e temperatura em diversos pontos do sistema, permitindo o registro dos fenômenos transientes que ocorrem durante a combustão, a possibilidade de programação e controle de tempos, pressões e temperaturas para testes de combustão e de pirólise através de rotinas especialmente desenvolvidas para isto, bem como a coleta representativa dos produtos sólidos e gasosos resultantes da combustão para posterior análise. É ainda possível a filmagem da xvi combustão em modo ultrarrápido, permitindo correlacionar as imagens aos dados termodinâmicos registrados durante a combustão ao longo de um segundo, em intervalos de poucos milissegundos. Os resultados iniciais obtidos na fase pré-operacional demonstram o bom funcionamento do sistema, permitindo distinguir claramente a influência da variação de parâmetros operacionais como tipo de carvão, massa e de amostra injetada, pressão e temperatura de operação e composição dos gases oxidantes. / Pulverized coal injection (PCI) is a technique used in blast furnaces (BFs) by Brazilian steel industry, following a worldwide trend, to reduce coke consumption by ton of hot metal produced, and therefore reducing the overall cost. Burning of pulverized coal injected into tuyeres of BFs takes place under medium pressure (up to 4 atm), high flame temperatures (around 2 000 °C), very fast heating rates (104–105 °C/s) and very short residence times, less than 40 ms, followed by gasification in presence of CO2. Since there are no standard tests for evaluation of coal combustibility at PCI conditions, lab and bench scale coal injection rigs and pilot plants are usually employed for this purpose. This work shows the development steps of a bench-scale rig, built at the Iron and Steelmaking Laboratory of the School of Engineering - Universidade Federal do Rio Grande do Sul (LASID-UFRGS), from the conceptual design to the pre-operational step, as well as the initial results. This equipment permits to study the combustion characteristics of coals in conditions very close to those occurring in blast furnaces. Initial tests include the combustion evaluation of a Brazilian coal, aiming its potential usage for PCI, in partial substitution of imported coals for this purpose. The rig has a modern design and is highly automated. Its scale and operational concept is fitted for academic studies. It has a vertical configuration, to be operated with injection of a coal sample in a single pulse mode and is capable to be adjusted afterwards to continuous coal injection mode. Some relevant characteristics of the injection rig are: (1) the very fast measurement and acquisition of thermodynamic data of pressure and temperature in several points of the system, allowing the capture of transient phenomena occurring along the combustion process; (2) the possibility of programming and controlling time intervals, pressures and temperatures to perform combustion and pyrolysis tests, employing specially developed routines; and (3) the representative sample collection of solid and gaseous combustion products to be further analyzed. It is also possible to capture images of the combustion by a high-speed camera, allowing correlate the images, acquired during a time interval of one second, with the thermodynamic data collected in intervals of few milliseconds. xviii The good performance of the equipment was shown by the initial results obtained at the pre-operational phase. The experimental data clearly depicted the effect of operational parameters like coal type, injected sample mass, operational pressure and temperature, and oxidizing gas composition.