O processo de injeção pelas ventaneiras dos altos-fornos (Pulverized Coal Injection - PCI) é uma das tecnologias mais promissoras para a incorporação de biomassas termicamente tratadas na siderurgia e um dos meios de alcançar uma redução consistente nas emissões de CO2 no setor. O objetivo deste trabalho foi avaliar a combustibilidade e reatividade ao CO2 de biomassas de madeira e caroço de azeitona tratadas em laboratório desde temperaturas de torrefação (250°C) até de carbonização (450°C) e comparar com carvões típicos utilizados em PCI, correlacionando com as características ocorridas devido aos tratamentos térmicos. Além da caracterização química, as transformações devido aos tratamentos térmicos das biomassas foram avaliadas via testes de combustão em termobalança, técnicas de microscopia ótica e eletrônica, espectroscopia de infravermelho por transformada de Fourier (FTIR) e técnicas de adsorção para análise da porosidade. Testes de combustibilidade foram conduzidos em um forno de queda livre (Drop Tube Furnace - DTF) em atmosferas convencional (O2/N2) e de oxi-combustão (O2/CO2) e os chars resultantes destes testes foram caracterizados quanto à estrutura e à reatividade ao CO2 em termobalança. Além disso, foram feitos testes de reatividade ao CO2 de misturas de eucalipto termicamente tratado e carvões em termobalança. A torrefação manteve o alto teor de voláteis das biomassas, enquanto que as biomassas carbonizadas apresentaram teores de carbono e poder calorífico semelhantes aos dos carvões de mais alto rank, com as vantagens típicas de biomassas de manterem um baixo teor de cinzas e enxofre. No entanto, o elevado teor de álcalis e fósforo nas cinzas pode ser um fator limitante na composição de misturas para PCI. O tratamento térmico das biomassas levou a gradual decomposição dos componentes da madeira com uma progressiva homogeneização da estrutura celular, associada a um aumento de aromaticidade e porosidade. De uma maneira geral, quanto menor foi a temperatura de tratamento térmico das biomassas, maior foi o burnout obtido no DTF. Comparada à atmosfera convencional (O2/N2), a atmosfera de oxicombustão (O2/CO2) levou a maiores burnouts para os chars de todas as biomassas e carvões. As biomassas carbonizadas apresentaram burnouts mais elevados que o carvão de mais baixo rank e o caroço de azeitona carbonizado apresentou baixa conversão, equivalente a um carvão de alto rank. Os chars das biomassas torrefeitas apresentaram estruturas cenosféricas isotrópicas de elevada porosidade nas paredes enquanto que os chars das carbonizadas preservaram a morfologia apresentada nas amostras originais. Os chars das biomassas foram altamente porosos, com áreas superficiais de meso e microporos em média 15 e 5 vezes maior que os chars dos carvões, respectivamente. Com relação aos testes de reatividade ao CO2 em termobalança, em geral, a reatividade dos chars das biomassas torrefeitas foi maior do que a reatividade dos chars das biomassas carbonizadas e estes foram pelo menos 10 vezes mais reativos ao CO2 do que o chars do carvão de mais baixo rank. Além das maiores áreas superficiais, principalmente o ordenamento da estrutura carbonosa e a morfologia foram fundamentais nas diferenças de reatividade ao CO2 entre os chars das biomassas e dos carvões. As misturas do carvão de mais baixo rank com a biomassa carbonizada apresentaram os melhores resultados em termos de aditividade na reatividade ao CO2. / Pulverized Coal Injection (PCI) in the blast furnace tuyeres is a promising technology for incorporation of thermally-treated biomasses and it is a way to reduce CO2 emissions in ironmaking processes. The aim of this work was to evaluate combustibility and CO2 reactivity of laboratory torrefied (250°C) and carbonized (450°) olive stone and woody biomasses, comparing with typical PCI coals. The transformations produced in biomasses due to torrefaction and carbonization were evaluated by chemical analyses, combustion tests in thermobalance, Fourier Transform Infrared Spectroscopy (FTIR) and optical and electron microscopy and adsorption techniques. Combustion experiments were carried out in a Drop Tube Furnace (DTF) under conventional (O2/N2) and oxy-fuel (O2/CO2) atmospheres and the chars collected were characterized by its structure and CO2 reactivity in thermobalance. Reactivity tests were also conducted in thermobalance with blends of thermally-treated eucalyptus and coals. Torrefied samples maintained high contents of volatile matter, typical of raw biomasses, while carbonized biomasses showed carbon contents and high heating values similar to that of high rank coals, retaining low ash and sulfur contents. However, its high alkali and phosphorus contents could be a limiting factor to the use in blends for PCI. The thermal treatments of biomasses lead to a gradual decomposition of wood components and to a progressive homogenization of cell structure, associated to an increase in aromaticity and porosity. In general, the lower the thermal treatment temperature, the higher was the burnout in the DTF. Compared to conventional atmosphere, oxy-fuel combustion led to the highest burnouts for all biomass chars. The carbonized biomasses showed higher burnouts than the high-volatile coal and olive stone showed burnouts similar to a low-volatile coal. The chars from the torrefied biomasses showed isotropic cenospheric structures with high porosity within the walls and the chars from the carbonized biomasses preserved the morphology seen in original carbonized samples. The biomass chars presented highly porosity, with micro and mesoporosity in average, 5 and 15 times greater than the coal chars, respectively. In relation to the CO2 reactivity tests, in general, the torrefied biomass chars were more reactive than the carbonized biomass chars. However, due to its higher surface areas, structure arrangement and morphology, the carbonized biomass chars were at least 10 times more reactive than the high-volatile coal chars. The blends of high-volatile coal and carbonized eucalyptus showed good additivity in the CO2 reactivity tests in thermobalance.

A presente pesquisa tem como objetivo desenvolver um novo elemento de cobertura, compatível com o meio ambiente: telhas de cimento alternativo reforçado com fibras celulósicas. Para tanto, foram utilizadas matérias-primas consideradas resíduos industriais (cimento de escória de alto-forno e rejeito de polpa de celulose de eucalipto) para obtenção de pastas cimentícias reforçadas. Os compósitos foram produzidos por dispersão prévia das fibras em água, mistura do compósito em argamassadeira convencional, adensamento por vibração, moldagem em fôrmas, seguida de cura úmida. Foram moldadas placas planas de diferentes formulações de matrizes cimentícias, com as matérias-primas alternativas disponíveis. Com base nos melhores resultados dessa fase preliminar, foram produzidas duas séries de telhas tipo romana \"capa canal\". Foram avaliados o desempenho físico-mecânico, os custos de produção e o comportamento térmico das telhas. Os resultados revelaram a potencialidade dos compósitos obtidos na produção de fibrocimentos alternativos, por meio de técnicas simples e de baixo consumo de energia, direcionados à autoconstrução urbana e rural de baixo custo. / The objective of this study was to develop a new roofing material that would be compatible with the environment: roofing tiles made of alternative cement reinforced with cellulose fibers. Industrial waste materials were used as raw materials (blast furnace slag cement and waste eucalyptus cellulose pulp) to obtain reinforced cement pastes. The composites were produced by previously dispersing the fibers in water, mixing the composite in a conventional cement-mixer, compaction by vibration, shaping them in molds, followed by moist curing. Flat sheets were molded using different formulations of cement matrixes with the alternative raw materials avaiable. Based on the best results from this preliminary phase, two series of Roman tiles for roofing were produced. The physical and mechanical performance, the cost of production, and the thermal behavior of the tiles were evaluated. The results revealed the potential of composites made of alternative fiber-cements, using simple techniques and with low energy consumption, in urban and rural areas for low-cost self-construction.

O uso de fibras vegetais e de cimentos alternativos – ambos provenientes de resíduos, é tido como boa opção na busca por novos fibrocimentos. Entretanto, a maioria das pesquisas desenvolvida nos últimos anos tem apresentado resultados desanimadores no que se refere à durabilidade do material. Além disso, os métodos para avaliação do desempenho ao longo do tempo de materiais reforçados com fibras sensíveis a álcalis ainda não estão bem estabelecidos. O trabalho avaliou o comportamento de compósitos produzidos com cimento de escória de alto-forno reforçados com fibras de celulose, moldados através de adaptações dos processos industriais usados em todo mundo pelas empresas de fibrocimento. Em seguida, a durabilidade das formulações foi avaliada através de ensaios de envelhecimento, os quais se basearam na simulação dos principais agentes e mecanismos de degradação atuantes no material. O desempenho físico e mecânico dos compósitos foi avaliado através da análise de propriedades pré-estabelecidas, consideradas importantes no emprego material como componente construtivo. A análise dos resultados confirmou a eficiência da incorporação da celulose nas propriedades mecânicas do compósito. A durabilidade do material foi diferente para as matrizes empregadas. As matrizes ativadas com gipsita e cal hidratada (EGCH) foram menos agressivas às fibras, entretanto apresentaram problemas de hidratação às primeiras idades e perda de resistência devido à carbonatação. A matriz ECP, mais alcalina, apresentou resultados superiores de resistência mecânica nas primeiras idades. Ela decompôs as fibras e reduziu as propriedades mecânicas durante o envelhecimento. A carbonatação reduziu o ataque alcalino às fibras nestas matrizes, estabilizando a resistência mecânica e a perda de tenacidade não foi tão acentuada. A metodologia de envelhecimento acelerado que combinou ciclos de molhagem e secagem à carbonatação se mostrou eficiente na simulação do envelhecimento natural. / Vegetable fibers and alternative cements from residues is a good option for replacement asbestos-cement. However, research development has presented no satisfactory results concerning material durability and methods of performance evaluation to reinforced materials with alcali sensitive fibers are not well developed. The objetives of this research are: a) evaluation of composites behavior produced with blast-furnace slag reinforced with residual cellulose fibers, which were moulded in adapted conventional industrial processes, common in fibercement companies around world and b) durability performance evaluation applying proposed aging tests. Aging tests were based on simulation of main agents and degradation mechanisms. Physical and mechanical behaviour of composites was evaluated considering important properties in building component uses. Cellulose fibers improved the mechanical properties of the composites. Durability presented different results for the two matrices. The matrices activated with gypsum and hidrated lime (EGCH) have been less aggressive than matrix activated with ordinary Portland cement (OPC) in relation to fibers. However, they presented problems concerning to the hydration at early dates and loss of resistance due to carbonation. Matrices activated with OPC presented better results of MOR at the early dates. In fact, they are more alkaline and they decomposed fibers and reduced the mechanical properties during the aging. The carbonation reduced the alkaline attack, stabilizing the MOR and reducing the loss of tenacity. The accelerated methods with carbonation were efficient in the simulation of the natural ageing.

As the largest source of iron in North America, and as the largest energy consumer in the modern integrated steel mill, the blast furnace is a critical part of modern ironmaking. Any improvements that can be made to the efficiency or emissions of the blast furnace can have far reaching environmental impacts as the production of one ton of steel results in 1.85 tons of carbon dioxide emissions. Given the concerted push to reduce greenhouse emissions, novel technologies are needed to improve efficiency. In this study the injection of preheated natural gas, precombusted syngas from a variety of feedstocks, and hydrogen injection were all modeled using computational fluid dynamics, from the tuyere through the shaft of the furnace. The impacts of these various operational changes were evaluated using CFD calculated analogs for Raceway adiabatic flame temperature (RAFT), top gas temperature (TGT), and coke rate (CR). Results indicate that a reduction of 3% to 12% in CO2 emissions is possible through the implementation of these technologies, with each possessing distinct benefits and drawbacks for industrial implementation.

This thesis deals with development of shrinkage reducing admixtures designed for alkali activated materials based on blast furnace slag. The main task of this work is to select the most suitable shrinkage reducing admixture based on experiments, in which can be observed minimal shrinkage and at the same time it will not adversely affect the properties of alkali activated blast furnace slag. In the experimental part of the work, test beams containing shrinkage reducing admixtures were prepared, in which the shrinkage and loss of weight were measured. Moreover, the mechanical properties of individual beams, such as tensile strength and compressive strength, were measured. Next, the surface tension of individual shrinkage reducing admixtures was measured in a mixture with pore solution. The hydration process of alkali activated materials under the action of reducing shrinkage admixtures was monitored by calorimetric analysis. The microstructure of the prepared samples was observed by scanning electron microscopy.

This diploma thesis is focused on methods of using cement kiln by-pass dust in building materials technology. By-pass dust was treated to remove chlorides and could then be used as other constituent to various types of cements in the amount of 0–5 wt. % according to ČSN EN 197-1. The properties of dusts before and after chloride removal were examined and after incorporating modified by-pass dust into the cement, the properties of fresh and hardened cement pastes and mortars were studied. It was found that modified by-pass dust after incorporation into cement fulfill requirements of ČSN EN 197-1.

Alkali-activated materials (AAM) are construction materials with great potential, especially for their environmental friendliness, but also due to their mechanical properties. Therefore, it is appropriate to pay further attention to these binders. This diploma thesis deals with monitoring the effectiveness of plasticizers in connection with the surface chemistry of the alkali-activated slag system. Sodium hydroxide and sodium water glass were used as alkaline activators for the preparation of alkali-activated blast furnace slag-based systems. To study the effectiveness of the lignosulfonate plasticizer, yield stress, heat flow, adsorption and zeta potential were monitored depending on the amount and time that the plasticizer was added to the system. The results show that the type of activator used in the mixtures plays an important role. NaOH-activated samples revealed the best efficiency of lignosulfonate plasticizers. A key factor in studying the behavior of the studied mixtures was the measurement of the zeta potential, which provided insight into the surface charge of blast furnace slag particles related to the ability of lignosulfonate to adsorb on grains of alkali-activated slag.

The aim of a diploma thesis is design of draft boiler for co-firing blast furnace gas and natural gas. In the first part is made the stoichiometric calculation for the gas mixture. Next is the proposal of combustion chamber and proposal of individual heating surfaces of boiler. Next part contains the thermal calculation and control of individual heating surfaces. Part of the work is also drawing documentation of boiler.

Aluminosilicate refractory grog are being manufactured by firing refractory clays, claystone and shale. Firing takes place mainly in rotary or blast furnaces. However, when adjusting the raw material before firing in blast furnaces, the formation of the fine clay particles takes place. It is not possible to fire the fine particles in blast furnaces the usual way, which leads to the generation of waste. There is a possibility, however, to form briquettes of these particles, which can be fired in blast furnaces. This solution also brings the possibility of adjusting the mixture by using correction raw materials or other types of clay. Using this method, it is possible to produce a special refractory grog with specific properties.

Alkali activated materials could be suitable alternative to construction materials based on ordinary Portland cement (OPC). Therefore, it is advisable to pursue these binders further on. Aim of this thesis is to clarify the effect of lignosulfonate-based plasticizer and polycarboxylate-based superplasticizer on the behaviour and nature of alkali activated materials. For the purposes of studying the efficiency of plasticizing additives, the change of workability of alkali activated blast furnace slag in dependence on time, effect of additives on mechanical properties as well as, with usage of isothermal calorimetry, their impact on kinetics of solidification and hardening had been observed. The stability of the plasticizing admixtures in a high alkaline environment such as water glass and sodium hydroxide had been studied using infrared spectrometry. As a last step, X-ray photoelectron spectroscopy (XPS) had been used while clarifying the chemical changes in the structure of plasticizing additives after adsorption to blast furnace slag.