A tecnologia de injeção de carvão pulverizado nas ventaneiras dos altos-fornos (PCI) é utilizada por siderúrgicas integradas no mundo inteiro visando a redução do consumo de coque e, consequentemente, a redução das emissões de CO2 e do custo do gusa. Como o Brasil é o maior produtor mundial de ferro- gusa em altos-fornos a carvão vegetal, torna-se grande o interesse pelo aproveitamento dos finos de biomassa gerados no processamento de carvão vegetal, a chamada moinha. Uma boa alternativa para aproveitamento dessa biomassa seria sua injeção em altos-fornos a coque. A alta combustibilidade é essencial para um carvão destinado à injeção, pois reduz a formação de char (carvão incombusto). Devido à dificuldade de queima completa na zona de combustão, o carvão a ser injetado deve gerar um char altamente reativo ao CO2, para que seja consumido na cuba do alto-forno, gerando gases termorredutores. Este trabalho teve por objetivo avaliar a combustibilidade e a reatividade ao CO2 de carvões e misturas binárias de finos de carvão vegetal com carvões fósseis visando PCI. O estudo se deu através de análise termogravimétrica (TGA). Foram utilizados três carvões fósseis de diferentes procedências e ranks para a formulação das misturas. Os carvões foram cominuídos abaixo de 90 μm, uma granulometria típica de injeção. Inicialmente fez-se uma avaliação da combustibilidade e da reatividade ao CO2 dos finos de carvão vegetal com o intuito de estabelecer a granulometria adequada para as misturas. Foi observado que basta o carvão vegetal estar em granulometria inferior a 1 mm para serem alcançados resultados superiores de combustibilidade e reatividade em relação aos carvões fósseis abaixo de 90 μm. A elaboração das misturas binárias foi feita, portanto, pela adição de carvão vegetal abaixo de 1 mm aos carvões fósseis abaixo de 90 μm. A elaboração das misturas binárias foi feita, portanto, pela adição de carvão vegetal abaixo de 1 mm aos carvões fósseis abaixo de 90 μm. As proporções testadas foram 10, 20 e 50% em massa de carvão vegetal. As misturas apresentaram um aumento de combustibilidade e de reatividade ao CO2 em relação aos carvões fósseis individuais. Além disso, considerando-se a composição química dos carvões em estudo em termos de teor de cinzas, matéria volátil, enxofre e poder calorífico, pode-se considerar que misturas binárias entre os carvões fósseis deste trabalho e moinha de carvão vegetal seriam satisfatórias para PCI nas proporções avaliadas. / The technology of pulverized coal injection into the blast furnace tuyeres (PCI) is used by integrated steel mills worldwide in order to reduce the consumption of coke and thereby the reduction CO2 emissions and the cost of pig iron. As Brazil is the world’s largest producer of pig iron in charcoal-based blast furnaces, it becomes great interest in the use of fine biomass generated during charcoal processing. A good alternative for harnessing this biomass would be the injection into coke-based blast furnaces. The high combustibility is essential for a coal to injection. Moreover, the char (unburnt coal) generated should be highly reactive to CO2, so that it is possible its consumption in the stack of the blast furnace, generating gas for iron ore reduction. This work aimed to evaluate the combustibility and reactivity to CO2 of binary blends of charcoal fines and coals with purpose to PCI. The study was carried out by thermogravimetric analysis (TGA). Three coals from different sources and ranks were used to the formulation of the blends. The coals were ground and sieved to a size less than 90 μm diameter. At first were done an assessment of combustibility and reactivity to CO2 of fines charcoal in order to set the suitable particle size to the blends. It was observed that charcoal less than 1 mm is enough to achieve superior results to those found in the coals below 90 μm. The proportions tested were 10, 20 e 50% by mass of charcoal. The blends showed an increase in combustibility and reactivity of its chars in relation to individual coals. Furthermore, considering the chemical of coals under study in terms of ash, volatile matter, sulfur and calorific value it can be considered that binary blends between the coals and charcoal of this work would be satisfactory to PCI in the proportions evaluated.

O uso de escória de alto forno como aglomerante alternativo ao cimento portland tem sido objeto de vários estudos no Brasil e no exterior. Além de representar vantagens ao meio ambiente por ser um resíduo, a escória apresenta boas possibilidades de emprego, principalmente pelo baixo custo e por suas vantagens técnicas das quais se destacam a elevada resistência mecânica, a boa durabilidade em meios agressivos, o baixo calor de hidratação. No entanto, o emprego deste material carece de estudos detalhados da retração, muito superior à do cimento portland. Este trabalho teve como objetivo estudar a cinética das retrações autógena e por secagem não restringidas do cimento de escória ativada em função, principalmente, do tipo e teor de ativadores empregados. Para a retração autógena, o corpo-de-prova foi selado com papel alumínio protegido internamente com plástico. As medidas estenderam-se de 6 horas até 112 dias. O fenômeno da retração também foi analisado com base nos resultados dos ensaios de porosimetria, calorimetria, termogravimetria e difração de raios X. Foram empregados como ativadores: silicato de sódio, cal hidratada + gipsita, cal hidratada e hidróxido de sódio. Como referência foi adotado o cimento portland da alta resistência inicial CPV-ARI. De acordo com os resultados obtidos, a ativação da escória com silicato de sódio apresentou retração por secagem e autógena superior à apresentada pelos demais ativadores e pelo cimento portland. A maior parte dessa retração medida ocorre até os 7 dias. A retração por secagem ocorre em dois estágios: o primeiro logo após a desmoldagem e o segundo a partir do início da formação dos produtos hidratados. O início da retração autógena coincide com o segundo estágio da retração por secagem. Com base nos ensaios de microestrutura, são determinantes para a elevada retração do cimento de escória ativada com silicato de sódio: a baixa porosidade, caracterizada pela predominância quase total de mesoporos; o elevado grau de hidratação e natureza dos produtos hidratados, com predominância quase total de silicato cálcio hidratado (C-S-H). Na ativação com cal e com cal mais gipsita, a composição diferente dos produtos hidratados (baixa formação de C-S-H e presença significativa de fases aluminato e sulfoluminato, respectivamente) altera a porosidade e a retração, principalmente a autógena que apresenta valores inferiores à do cimento portland. A ativação com hidróxido sódio é caracterizada pela elevada retração autógena e baixa formação de C-S-H, com presença significativa de fases aluminato. / The use of ground granulated blast furnace slag (BFS) as an alternative binder to portland cement has been the subject of numerous studies in Brazil and other countries. Because BFS is a residue, its use benefits the environment. Furthermore, BFS cement is less costly and shows technical advantages if compared with normal portland cement, namely the higher strength, good durability in aggressive environments, and low heat of hydration. On the other hand, the high shrinkage of BSF cement is often indicated as one of the major limiting aspects for its use. The objective of this research was to study the development of unrestrained autogenous and drying shrinkage of BSF cement as function, mainly, of the chemical activator types and dosages. Autogenous shrinkage was measured in fully aluminum foil and plastic sheet wrapped specimens. Measurements were taken from 6 hours up to 112 days. Shrinkage was also analyzed in conjunction with mercury posorimetry, conduction calorimetry, thermogravimetric analysis and X-ray diffraction tests. Activators used were sodium silicate, hydrated lime + gypsite, hydrated lime and sodium hydroxide. High early strength portland cement was used as reference. The results showed that autogenous and drying shrinkage were larger when BFS was activated with sodium silicate. Most of the shrinkage occurs before 7 days of hydration. Drying shrinkage occurs in two phases: the first phase immediately after demolding, and the second phase concurrently with the formation of the hydrated products. Autogenous shrinkage coincides with the second phase of the drying shrinkage. Based on microstructure analysis, determining factors could be identified that respond for the high shrinkage of sodium silicate activated BFS cement: low porosity, mostly mesopores; high degree of hydration and chemical nature of the hydrated products, essentially calcium silicate hydrate - C-S-H. Activation with hydrated lime and hydrated lime plus dehydrated calcium results low amounts of C-S-H and significant quantities of aluminate and sulphoaluminate phases, respectively. Porosity and shrinkage, mainly autogenous, are lower than that verified for portland cement mixtures. Activation with sodium hydroxide causes high autogenous shrinkage, small amounts of C-S-H and significant quantities of aluminate phases.

The enrichment of alkali in the blast furnace has been proven to be a catalyst of coke gasification and is thus a key parameter in the degradation of coke. Alkali also directly destroys the carbon structure, increases the risk of scaffold formation, increases the load and attacks the refractory. It is thus important to decrease the recirculation of alkali in the blast furnace and the gasification of coke to ensure sufficient strength of the coke. The aim of the present study was to examine possible ways of alkali control in the blast furnace. This was done by investigating if coke with a modified ash composition contributed to a higher capacity of binding alkali in stable phases, which can be drained via the slag. This would decrease the recirculation of alkali in the blast furnace and prohibit coke degradation. Two campaigns were studied to determine the distribution of alkali in the shaft when the charging differed, this to improve the understanding of alkali control in the blast furnace with respect to the charging practice. Three different test cokes were produced in pilot scale with a mineral addition of kaolin, silica or bauxite. The test cokes were together with base coke used as a reference, charged in baskets to LKAB’s Experimental Blast Furnace (EBF) at the end of a campaign. When the campaign was finished the EBF was quenched with nitrogen and the charged baskets were excavated. The influence of alkali on coke with a modified ash composition was examined with XRF, XRD, SEM-EDS and TGA. This was done in order to confirm any difference between the test cokes and the base coke in terms of chemical composition, phases in the coke ash, degree of graphitisation and reactivity. The results showed that the base coke in most cases had collected more alkali compared to the test coke with a mineral addition of kaolin and silica. For the test coke with addition of bauxite the alkali content was higher in three out of four samples compared with the corresponding base coke. Unreacted grains with bauxite were detected, which indicates that bauxite was completely or partly inactive in the capturing of alkali. All aluminosilicates detected in the coke samples contained alkali, which indicates that aluminosilicates contributes in the capturing of alkali in the EBF. The main mineral phases containing potassium in the coke were kalsilite, leucite and other aluminosilicates with varying alkali content. The carbon conversion and thus the reactivity increased with the alkali content in both the test coke and the base coke. The reactivity of the test coke was thus not decreased due to the mineral addition. No indications of an increased capacity of capturing alkali in stable phases could be seen in the test cokes, this could be due to the low amount of minerals added. The uptake of alkali in the different coke types was dependent of the horizontal and vertical position in the EBF, and thus the conditions the baskets had been exposed to and the distribution of alkali within the EBF. It was concluded that the charging had an impact on the alkali distribution in the EBF. During campaign 31 the alkali content was more evenly distributed over the horizontal section in the upper part of the furnace, in the lower shaft the alkali content increased towards the centre. During campaign 32 the alkali content was increasing towards the walls in shaft of the EBF. The content of alkali in the lower shaft was higher during campaign 32 compared with campaign 31.

This thesis deals with the design of a co-combustion gas boiler for coal gas and blast furnace gas mixture. The calculation includes stoichiometry, determinination of the boiler efficiency, steam production rate and heating surfaces sizing. This thesis also includes technical documentation of designed gas boiler. The calculation of the boiler meets the values specified by the scripts and also by documentation from PBS. The boiler was designed for 113.9 MW and 93.77 % efficiency.

The aim of this diploma thesis is to design a gas boiler for blast furnace gas combustion. At the beginning is performed stoichiometry of the used fuel to determine the optimal amount of combustion air and the actual amount of flue gas. Subsequently is determined the overall efficiency, together with heat and steam power of the boiler. The main part of the thesis is focused on the design of the combustion chamber and the dimensioning of heat exchange surfaces. At the end of the thesis are performed hydraulic and aerodynamic calculations to determine the pressure loss on the side of the working medium and flue gas. Drawing documentation can be found in attachments.

The carbonation of the building materials based on the ordinary Portland cement is relatively well-known and extensively studied phenomenon. Conversely mechanism, reaction products and factors affecting the carbonation of the alkali activated materials are still not sufficiently clarified. In this work, the progression of the carbonation of the alkali activated materials under different conditions was investigated. The reaction products and the microstructural changes were determined by XRD respectively SEM-EDX analysis. The corrosive conditions due to the decreasing of the pH of the binders by the carbonation were observed by XPS analysis of the steel fibers. The carbonation of the alkali activated samples was compared with the reference samples based on the Portland composite cement. Besides these analyzes, the mechanical properties of the binders were monitored.

This thesis is focused on the principles of behavior of shrinkage reducing agents (SRA) in alkali-activated materials based on blast furnace slag. The main focus of this work is selecting the most suitable admixture based on experiments, by which will be achieved through minimal shrinkage and will have negative effect on the properties of alkali-activated blast furnace slag at the same time. In experimental section of this work, the surface tension as individual additives as their mixtures with pore solution were measured primarily. Then the testing samples composed of blast furnace slag, water glass and addition of SRA were prepared. Of these samples was measured shrinkage and weight loss. Moreover, their mechanical properties such as flexural and compressive strength were monitored. Next, the beginning and the end of solidification was studied using the Vicat device and last but not least workability. The hydration process of alkali-activated materials with SRA was measured calorimetrically. Finally the microstructure in prepared samples was observed using scanning electron microscopy (SEM-EDS) and the total porosity was determined by mercury porosimeter.

This report is about continuous temperature measurements of pig-iron at tapping from blast furnace 2 in Oxelösund, SSAB. Nowadays the temperature is only checked once at every tapping. The purpose of this project is to see if the process stability increases by continuously knowing the temperature and to compare the costs of this new technique with the technique used today. Possible savings due to less consumption of coke/coal if the silicon amount and the temperature are closer to their aim values will be regarded and if as little steam consumption as possible are used. The process stability can be divided into different sub goals. The ordinary measuring techniques were investigated as a part of the main goal; such as the ordinary measured temperature, the pig-iron and slag samples. The new continuous temperature measuring technique was compared with the ordinary temperature measurement and investigations of the life length were done. How representative the pig-iron and slag samples are, when taking them at the time they are today, are also looked into. The continuous measured temperature showed around 0,37 % higher temperature than the ordinary measured temperature. The pig-iron and slag samples should be taken as they are today, for mainly safety aspects. By using continuous temperature measurement, some of the sub goals can be achieved for a more stable process. The economy on the other hand has shown that large savings can be done by using this continuous temperature method due to a more stable process. This is mainly because of a decrease in steam usage in the experimental period. By regarding only the material of the methods the continuous temperature equipment is a bit more expensive, but the savings are much larger so the continuous temperature method is beneficial. With time this method could probably improve the process stability even more since the operators will deal with the information and the probe better.

This study has focused on determining the heat flows in a production blast furnace hearth. This part of the blast furnace is exposed to high temperatures. In order to increase the campaign length of the lining an improved knowledge of heat flows are necessary. Thus, it has been studied both experimentally and numerically by heat transfer modeling. Measurements of outer surface temperatures in the lower part of a production blast furnace were carried out. In the experimental study, relations were established between lining temperatures and outer surface temperatures. These relations were used as boundary conditions in a mathematical model, in which the temperature profiles in the hearth lining are calculated. The predictions show that the corner between the wall and the bottom is the most sensitive part of the hearth. Furthermore, the predictions show that no studied part of the lining had an inner temperature higher than the critical temperature 1150°C, where the iron melt can be in contact with the lining. / QC 20101124

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 physicochimiques 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. / 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.