O pó de aciaria elétrica é um importante subproduto da indústria siderúrgica devido ao seu alto teor de zinco. Assim, tecnologias vêm sendo desenvolvidas visando seu aproveitamento, sendo o forno Waelz a mais difundida delas atualmente. No entanto, sua operação, por contar com um forno rotativo de grandes dimensões que abriga uma infinidade de fenômenos físico-químicos, apresenta difícil previsibilidade ab initio. Por essa razão, este trabalho faz uso de uma ferramenta avançada da termodinâmica computacional, destinada à modelagem de processos, chamada SimuSage, a fim de modelar o seu comportamento. Para a criação do modelo utilizou-se também uma base de dados termodinâmicos advinda do software FactSage e a plataforma de desenvolvimento Lazarus. Com base em dados e resultados operacionais da literatura, foi possível realizar simulações nos modos adiabático e isotérmico, comparando os resultados com os da prática industrial. Constatou-se uma grande capacidade do modelo de reproduzir os resultados da literatura, mesmo quando não há muita informação para aferição dos parâmetros, gerando boa concordância com a composição química relatada dos produtos Óxido Waelz e Escória Waelz. / The electric arc furnace dust is an important by-product of the steel industry due to its high content of zinc. Thus, technologies have been developed aiming for its use, and the Waelz Kiln is the most widespread of them today. However, counting on a very large rotary kiln that houses an infinity of physico-chemical phenomena, its operation is difficult to predict ab initio. For this reason, in order to model its behaviour this work uses an advanced tool of computational thermodynamics designed to process modelling, called SimuSage. To create the model, a thermodynamic database, provided by the FactSage software, as well as a development platform, Lazarus IDE, were also used. Based on operational data and results from de literature, it was possible to perform simulations on both adiabatic and isothermal modes comparing its results with the industrial practice. A great capability of the model to reproduce results from the literature was found, even when there is not much information for the parameters calibration, generating good agreement regarding the reported chemical composition for the products, Waelz Oxide and Waelz Slag.

A presente tese teve como objetivo fornecer subsídios teóricos e experimentais com vistas à reciclagem da carepa gerada em usinas mini-mills através de briquetes autorredutores para uso em FEA. Para atingir os objetivos vislumbrados, o trabalho foi estruturado em quatro principais tópicos: estudo de caracterização e de redutibilidade da carepa, escolha e caracterização do redutor para uso nos briquetes, elaboração e caracterização da mistura e ensaios de laboratório para avaliação do desempenho dos briquetes autorredutores. Os estudos de caracterização da carepa indicaram que este resíduo é constituído principalmente de wustita e se apresenta estratificada em três camadas: camada externa fina e porosa composta de hematita e magnetita, camada intermediária de wustita densa e camada interna de wustita porosa. A cinética de redução da carepa foi investigada em termobalança no intervalo de temperatura entre 830 e 1200°C com CO puro e mistura 90%CO-10%CO2. A energia de ativação aparente encontrada nesses ensaios variou de 71 a 80 kJ/mol e as observações microscópicas demonstraram que a redução da carepa segue um modelo topoquímico. A escolha do agente redutor para compor o briquete se deu através de ensaios de gaseificação ao CO2 e de autorredução em termobalança com três tipos de material carbonoso. A partir desses ensaios observou-se a seguinte ordem decrescente de reatividade e respectivas energias aparentes de ativação: Carvão Vegetal (Ea = 237 kJ/mol), Carvão Mineral (Ea = 214 kJ/mol) e Coque de Petróleo (Ea = 335 kJ/mol). Em virtude da maior reatividade do Carvão Vegetal frente aos demais, este redutor foi escolhido para uso nos briquetes. A mistura utilizada na confecção dos briquetes autorredutores teve como constituintes principais a carepa, os finos de carvão vegetal e aglomerantes (melaço e cal). Ensaios de caracterização em termobalança com atmosfera oxidante e aquecimento rápido indicaram uma perda de massa de cerca de 40%, referente às etapas de secagem, desvolatilização e autorredução da mistura. Nesses ensaios, observou-se elevadas taxas de perda de massa da mistura e uma notável complexidade dos fenômenos envolvidos, com reações simultâneas de combustão, autorredução e de oxidação do ferro, prevalecendo uma ou outra, dependendo da temperatura e da fração reagida de amostra. Através de procedimentos que buscaram reduzir a complexidade dos fenômenos envolvidos nas condições oxidantes, foi possível estimar que a energia de ativação aparente de autorredução está entre 62 e 69 kJ/mol. Os briquetes produzidos em escala industrial foram submetidos a ensaios isotérmicos e não-isotérmicos de alta temperatura. Tais ensaios buscaram determinar os gradientes térmicos no interior do briquete, a energia de ativação aparente e o desempenho cinético do aglomerado em condições de temperatura que se aproximam da prática industrial. A partir das constatações concernentes às taxas das reações químicas individuais (redução e gaseificação), às medidas do perfil de temperatura no interior dos aglomerados, à energia de ativação estimada para o briquete (93 kJ/mol) e ao modelo de redução encontrado nos ensaios de alta temperatura, acredita-se que tanto a cinética de redução da carepa como a transferência de calor sejam obstáculos limitantes da cinética global dos briquetes em estudo. Finalmente, os resultados de metalização obtidos nos testes de alta temperatura dão indícios da possibilidade de uso destes briquetes em FEA. / This dissertation aimed to provide theoretical and experimental basis for recycling of mill scale generated in mini-mill plants through the use of self-reducing briquettes in EAF. To reach these goals, the work was structured around four main topics: characterization and reducibility study of scale, choice and characterization of the reductant to use in briquettes, elaboration and characterization of the mixture and laboratory tests to performance evaluation of self-reducing briquettes. The characterization studies of mill scale have indicated that this waste is composed mainly of wustite and is stratified into three layers with different morphologies: fine porous external layer composed of hematite and magnetite, intermediate layer of dense wustite and inner layer of porous wustite. The kinetics of scale reduction was investigated in thermobalance in a temperature range from 830 to 1200°C with pure CO and a mixture of 90% CO and 10% CO2. The apparent activation energy obtained in these tests ranged from 71 to 80 kJ/mol and the microscopic observations showed that the mill scale reduction corresponds to a topochemical model. The choice of the reductant for composing the briquette was made through tests of gasification with CO2 and of self-reduction in thermobalance with three different carbonaceous materials. From the results, it was observed the following decreasing reactivity order and the related apparent activation energy: Charcoal (Ea = 237 kJ/mol), Mineral Coal (Ea = 214 kJ/mol) and Petroleum Coke (Ea = 335 kJ/mol). Due to the higher reactivity of Charcoal in relation to the others, this reducer was chosen to be used in the briquettes. The main constituents of the mixture used in the manufacture of self-reducing briquettes were scale, charcoal and binders (melasse and lime). The characterization tests in thermobalance with oxidizing athmosfere and rapid heating indicated a mass loss of about 40%, referring to the stages of drying, devolatilization and self-reduction of the mixture. During these tests, it were observed high rates of mixture loss mass and a remarkable complexity of the phenomena, with simultaneous combustion, self-reduction and iron oxidation reactions, where their importance changes according to temperature and fractional reaction of the sample. Through the procedures that aimed to reduce the complexity of the related phenomena in oxidant conditions, it was possible to estimate that the self-reduction apparent activation energy ranges between 62 to 69 kJ/mol. The briquettes produced in the industrial plant were submitted to isothermal and nonisothermal tests of high temperatures. Such tests aimed to determine the thermal gradients into the briquette, the apparent activation energy and kinetic performance of the agglomerate in temperature conditions similar to the ones used in industrial practice. Based on the findings concerning the individual rates of chemical reactions (reduction and gasification), the measures of the temperature profile inside the briquettes, the activation energy estimated (93 kJ/mol) and the reduction model found in high-temperature tests, it is assumed that both the kinetics of mill scale reduction and heat transfer limit the overall kinetic rates of these briquettes. Finally, the results of metallization obtained in the tests conducted at high temperatures indicate the possibility of using these briquettes into the EAF.

This thesis centers around an electric arc furnace (EAF) at a steel mini-mill in Wilton, IA. First, the thesis replicates previous optimization attempts. Next, the modeling is greatly altered to produce a much improved steel-melting model. Then, a new optimal control system is created and used to reduce energy and fuel costs over the melting process. Finally, results are presented. This thesis shows that when the new optimal control is simulated, the system shows significant energy and fuel savings.

Voltage (lighting) flicker is mainly caused by the electric arc furnaces (EAF) facility supplied by the medium and high voltage power network. In addition to that, because of the increase of wind power generation in both quantity and capacity, intermittent power output of wind turbines under wind speed variation could also cause voltage flickers that affect the performance of lighting and electronics devices in the neighboring feeder buses. Successful voltage flicker prediction and propagation estimation would help both utility and customers in dealing with the problem. This dissertation presents a nonlinear model for the short term prediction of voltage flicker due to EAF operations. In this study, synchronized voltage flicker measurement was conducted at several EAF facilities to understand the stochastic behavior of voltage flicker. The electric loading condition during EAF melting process shows a long term qualitative behavior of a dynamic system and illustrates a special structure of a fractal system. With the fractal structure identification, the behavior hidden behind the voltage flicker time series measurement could be grasped. Using a phase space reconstruction technique and Lyapunov exponent (LE) of state trajectory in the phase space, based on actual voltage flicker measurements, it is proved that the voltage flicker time series is chaos. By using LE, three formulations are adopted to build the prediction models and illustrate the feasibility of short term EAF voltage flicker prediction. Currently, some Asian countries are using the Japanese £GV10 flicker voltage standard. Due to the adoption of IEC standard by IEEE and European countries, a rational conversion of flicker planning limits between different standards would help utilities consider revising or changing their voltage flicker standards and planning limits. Statistical analyses of Pst and £GV10 measurement are conducted in this study. Under different EAF types and operation conditions, reasonable conversion factors between Pst and £GV10 standards are derived, and the flicker transfer factor between different voltage levels of the power supply system are presented.

The electric arc furnace steelmakers produce steel across wide ranging sizes and different quality levels. The method of using electric arc for melting is an important process to produce steel from iron or scraps. The diversity of products and markets makes the steelmakers to operate within a large number of constraints of limited enterprise resources, so the electric arc furnace manufacturing system faces problems to integrate the enterprise resource planning system with the manufacturing execution system. The international automation society has come out a solution with an international standard, also known as ISA-95 aimed to help manufacturing industries such as electric arc furnace steelmakers, for the integration of enterprises and control systems. However, ISA-95 only emphasizes on the integration of enterprises and control systems, but does not provide a whole picture of the entire system. This research utilizes the tool of system architecture to develop the architecture-oriented electric arc furnace manufacturing system model, abbreviated as AOEAFMSM, to illustrate coherently the structure view and the behavior view of the electric arc furnace manufacturing system. Furthermore, AOEAFFMSM is able to fully describe many other views of the electric arc furnace manufacturing system. This capability satisfies everybody¡¦s need for capturing different views of the system. Consequentially, AOEAFFMSM simplifies the software development and reduces many communication difficulties among system developers and customers. In modeling the electric arc furnace manufacturing system model, AOEAFFMSM is superior to ISA-95.

Στην παρούσα εργασία, εξετάστηκε η δυνατότητα χρήσης της σκωρίας κλιβάνου ηλεκτρικού τόξου (Electric Arc Furnace Slag- EAFS), ως πρώτη ύλη στη διεργασία παραγωγής τσιμέντου μπελιτικού τύπου. Η σκωρία κλιβάνου ηλεκτρικού τόξου (EAF) είναι ένα παραπροϊόν της μεταλλουργικής βιομηχανίας. Προκύπτει από την τήξη σε κλίβανο ηλεκτρικού τόξου (Electric Arc Furnace - EAF) παλαιοσιδήρου (ferrous scrap). Σύμφωνα με την American Society for Testing Materials (ASTM), η σκωρία ορίζεται ως ένα μη μεταλλικό προϊόν. Η σκωρία είναι ένα τήγμα που αποτελείται κυρίως από πυριτικές ενώσεις του ασβεστίου ενωμένες οξείδια σιδήρου, αλουμινίου, ασβεστίου και μαγνησίου και παράγεται ταυτόχρονα με τον χάλυβα μέσα σε κλίβανο. Η ποσότητα σκωρίας που παράγεται στα χαλυβουργεία, ως παραπροϊόν της παραγωγικής διαδικασίας, αποτελεί ποσοστό περίπου 13% - 18% επί της συνολικής ποσότητας τροφοδοσίας του κλιβάνου με αποτέλεσμα οι μεταλλουργικές σκωρίες να είναι ένα από τα μεγαλύτερα σε ποσότητα βιομηχανικά παραπροϊόντα. Ως συνέπεια, οι χαλυβουργίες αντιμετωπίζουν προβλήματα απόθεσης και διάθεσης των σκωριών καθώς και τις περιβαλλοντικές επιπτώσεις που προκύπτουν από αυτά. Μια κατηγορία τσιμέντων για την οποία υπάρχει έντονο ενδιαφέρον τα περίπου τελευταία 20 χρόνια είναι τα μπελιτικά τσιμέντα, καθώς παρουσιάζουν μειωμένη, θερμοκρασία έψησης και εκπομπή CO2. Η διαφορά των ανωτέρω τσιμέντων με τα τσιμέντα τύπου Portland είναι τα μειωμένα επίπεδα της φάσης του πυριτικού τριασβεστίου (C3S), απόρροια της χαμηλής θερμοκρασίας έψησης (~1350°C) γεγονός που τα κατατάσσει στην κατηγορία των φιλικών προς το περιβάλλον τσιμέντων. Επιπρόσθετα η αξιοποίηση παραπροϊόντων ως A! Ύλες, που παρουσιάζουν χημική σύσταση κατάλληλη για την παραγωγή τσιμέντου, οδηγεί σε μερική μείωση της ζήτησης Α! υλών και σε ελάττωση των εκπομπών CO2, καθώς αποτελούν πηγή CaO ελαττώνοντας την ανάγκη για απανθράκωση του CaCO3. Μελετήθηκε η δυνατότητα προσθήκης σκωρίας EAF ως Α! ύλης για την παραγωγή τσιμέντων μπελιτικού τύπου. Οι πρώτες ύλες που χρησιμοποιήθηκαν για την προετοιμασία των μιγμάτων ήταν ασβεστόλιθος, αργιλικός σχιστόλιθος καθώς και σκωρία κλιβάνου ηλεκτρικού τόξου (EAF). Η EAFS προήλθε από την χαλυβουργία «SOVEL» (θυγατρική της «ΣΙΔΕΝΟΡ») της οποίας η ετήσια παραγωγή σε χάλυβα είναι 750 kt ενώ σε EAFS 97.5 kt. Οι πρώτες ύλες αναλύθηκαν ως προς την χημική τους σύσταση με τη χρήση φθορισμομετρίας ακτίνων X (XRF, Philips PW 2400) και προσδιορίστηκε η ορυκτολογική τους σύσταση μέσω περιθλασιμετρία ακτίνων Χ (XRD, D5000 Siemens) ποιοτικά και ποσοτικά (QXRD, μέθοδος Reitveld). Για τη σκωρία πραγματοποιήθηκε παρατήρηση της μικροδομής της καθώς και στοιχειακή ανάλυση με ηλεκτρονική μικροσκοπία σάρωσης (SEM-EDS), βάση των οποίων κρίθηκε κατάλληλη να υποκαταστήσει μέρος των Α! υλών στην παραγωγή τσιμέντου . Τέσσερεις τύποι clinker παρήχθησαν με 0κ.β.% (BC), 5κ.β.% (BC5) 10κ.β.% (BC10) και 20κ.β.% (BC20) σκωρία EAF με στόχο την διατήρηση του μπελίτη σε υψηλή περιεκτικότητα (>55%). Η έψηση των clinker πραγματοποιήθηκε στους 1380ºC. Η θερμοκρασία έψησης προσδιορίστηκε από προκαταρκτικές δοκιμές έψησης στο θερμοκρασιακό εύρος 1280°C-1400°C, με βάση τα αποτελέσματα της ελευθέρας ασβέστου και την εξέλιξη της μικροδομής. Η μικροδομή των παραγόμενων clinker αποτελείται κυρίως από κρυστάλλους μπελίτη και αλίτη, ενώ η ρευστή φάση (C3A+C4AF) παρουσιάζεται ως μήτρα γύρω από τους κρυστάλλους με λεπτοκρυσταλλική δομή. Τα παραγόμενα τσιμέντα υστερούν σε πρώιμες αντοχές. Εντούτοις, τα αποτελέσματα των αντοχών για τις 28 ημέρες που για τα BC, BC5, BC10 και BC20 είναι 47.5 MPa, 46.6 MPa , 42.8 MPa και 35.5 MPa αντίστοιχα πληρούν τις προϋποθέσεις για ένταξή τους στην κατηγορία OPC CEMI 32.5N, σύμφωνα με το EN 197-1. Παρατηρήθηκε επίσης, ότι τα BC10 και BC20 συμπεριφέρονται ως ταχύπηκτα, ενώ η υγεία σε όλες τις περιπτώσεις δεν υπερβαίνει το 1mm. Τα αποτελέσματα δείχνουν ότι η σκωρία EAF μπορεί να χρησιμοποιηθεί για την παραγωγή των εν λόγω τσιμέντων αλλά και ότι τα τσιμέντα αυτού του τύπου υστερούν στην ανάπτυξη των πρώιμων αντοχών έναντι των Portland. Επίσης, παρασκευάστηκαν 6 blended τσιμέντα, με ανάμιξη με BC, BC5 και BC10 σε διάφορα ποσοστά, με OPC_42.5Ν. Τα blended τσιμέντα έδωσαν βελτιωμένες συνολικά αντοχές. Οι πρώιμες αντοχές παρουσίαζαν μικρή μείωση σε σχέση με το OPC_42.5N. Ελέγχθηκε κατά πόσο το τελικό προϊόν που παράγεται μέσω της πειραματική-εργαστηριακής διαδικασία αποκλίνει ποιοτικά από αυτό που έχει προέλθει από την βιομηχανική παραγωγική διαδικασία, και τα αποτελέσματα ήταν ικανοποιητικά. Όσον αφορά τις βιομηχανίες τσιμέντου και χάλυβα, η παραγωγή μπελιτικών τσιμέντων με παράλληλη αξιοποίηση σκωρίας ως Α! ύλη συνεπάγεται κέρδος τόσο περιβαλλοντικό όσο και οικονομικό. Συνολικά κατά την παραγωγή τους απαιτείται λιγότερη ενέργεια, εκπέμπεται μικρότερη ποσότητα CO2 και η ζήτηση σε πρώτες ύλες είναι επίσης μειωμένη. Η μελέτη της περιβαλλοντικής συμπεριφοράς των BC5 και BC10 τσιμέντων, πραγματοποιήθηκε με βάση το πρότυπο NEN 7345-tank test που αναφέρεται σε μονολιθικά υλικά. Τα αποτελέσματα δείχνουν ότι στην περίπτωση του V δεν ανιχνεύεται καμία μετρήσιμη εκλουόμενη ποσότητα για τα δύο δοκίμια ενώ στην περίπτωση του Cr η συνολική έκλουση που καταγράφεται μετά από 64 ημέρες είναι 78.72 mg/m2 για το BC5 και 113.81 mg/m2 για το BC10. Οι τιμές του εκλουόμενου Cr και για τα δυο δοκίμια, δεν υπερβαίνουν το όριο Existing (NEN7375) Monolithic Waste Acceptance Criteria_mg/m2 at 64 days (500 mg/m2), σύμφωνα με τον moWaC. Ο προσδιορισμός του μηχανισμού που οδηγεί στην απελευθέρωση χρωμίου για τα δοκίμια προσδιορίστηκε ότι είναι διάχυση. / In the present work studied the valorization of the electric arc furnace slag (Electric Arc Furnace Slag-EAFS), as raw material in the production of belite cement. The electric arc furnace slag (EAF) is a byproduct of the metallurgical industry, resulting from melting in electric arc furnace ferrous scrap. According to the American Society for Testing Materials (ASTM), the slag is defined as a non-metallic product. The slag is a molten phase consisting mainly of calcium silicate compounds joined together with oxides of iron, aluminum, calcium and magnesium and is produced simultaneously with steel in a furnace. The quantity of slag produced in steel industries, as a byproduct of the production process, represents approximately 13% - 18% of the total quantity supplied to the furnace so that the metallurgical slag is one of the major industrial products in quantity. As a result, steel industries are facing problems with the deposition and disposal of the slag and the environmental impacts arising from them. The scientific interest over the last 20 years was turned to the production of belite cements, which present low firing temperature and CO2 emission. This type of cement, unlike conventional OPC, contains a higher percentage of belite (C2S) and a lower percentage of alite (C3S), result of low firing temperature (~1350°C) which classifies them in the category of environmentally friendly cements. Additionally, the valorization of industrial byproducts, as raw materials, which present chemical composition suitable for cement production, leads to partial reduction of raw materials demand and CO2 emissions, as they constitute source of CaO by reducing the need for decarbonation of CaCO3. The valorization of EAF slag as raw material in the producing of belite cement was studied. The raw materials used to prepare the mixtures were limestone, clay and EAF slag. The EAF slag derived from the steel industry «SOVEL» (subsidiary of "Sidenor") which annual production of steel is 750 kt while EAF slag is 97.5 kt. Their chemical analysis was performed by X-ray fluorescence spectrometry (XRF, Philips PW 2400). The crystalline phases of the raw materials were identified by X-ray diffraction analysis (D5000 Siemens). Qualitative analysis was performed by the DIFFRACplus EVA® software (Bruker-AXS) based on the ICDD Powder Diffraction File. The mineral phases were quantified using a Rietveld-based quantification routine with the TOPAS® software (Bruker-AXS). The slag was characterized by SEM/EDS micro-analysis, results shown that was appropriate to partially substitute the raw materials in cement production. Four types of clinker produced with 0w.t.% (BC), 5 w.t.% (BC5), 10 w.t.% (BC10) and 20 w.t.% (BC20) EAF slag, aimed at maintaining high belite (> 55%) levels. The firing temperature of the clinker was at 1380ºC. The firing temperature was determined by preliminary burnability tests at the temperature range of 1280°C-1400°C, based on the results of free lime content and the microstructure evolution. The microstructure of the produced clinker consisting mainly of belite and alite crystals, while the (C3A + C4AF) is presented as an interstitial phase around the crystals with micro-crystalline structure. The produced cements present low early strength. However, the strength results of 28 days for BC, BC5, BC10 and BC20 are 47.5 MPa, 46.6 MPa, 42.8 MPa and 35.5 MPa respectively, meet the conditions for integration into the category OPC CEMI 32.5N, according to EN 197-1. Also observed that the BC10 and BC20 behave as ‘‘flash-set’’ cements. The expansion (soundness) was measured 1mm for all the samples. The results show that the EAF slag could be used for the production of such cements, which disadvantage in the development of early strength towards OPC. Moreover, 6 blended cements prepared by mixing BC, BC5 and BC10 at different proportions, with OPC_42.5N. The blended cements provided improved overall strength. The early strength showed a slight decrease compared with OPC_42.5N. Was examined the qualitative difference of the cement which was produced by laboratory-experimental procedure with the one from the industrial production process, the results were satisfactory. With regard to cement and steel industries, belite cements production with parallel valorization of EAF slags as raw material implies both environmental and energy profits. Overall their production requires less energy, less amount of CO2 emitted and also the demand of raw materials is reduced. The study of the environmental behavior of BC5 and BC10 cement, carried out according to the NEN 7345-tank standard test referred to monolithic materials. The results showed no V release, while the release of Cr increased according with the increment of the slag content. The total leached quantity after 64 days is 78.72 mg/m2 for BC5 and 113.81 mg/m2 for BC10. The values of the leachate Cr for both samples, not exceeding the limit of Existing (NEN7375) Monolithic Waste Acceptance Criteria_mg/m2 at 64 days (500 mg/m2). The determination of the mechanism leading to the release of chromium samples, determined to be diffusion.

O setor siderúrgico, assim como os demais setores da indústria, vem buscando alternativas para a redução dos custos de produção e aumento de produtividade. Em aciarias elétricas, os principais custos de produção do aço podem ser divididos, de forma simplificada, entre o custo dos insumos e o custo das matérias primas. Os refratários estão entre os cinco maiores custos na produção do aço em usinas semi-integradas. Entretanto, o conhecimento detalhado da microestrutura e do comportamento desses materiais ainda é bastante restrito aos seus fabricantes. Tendo em vista a importância dos refratários na produção do aço, este trabalho teve como objetivo gerar conhecimento acerca de sua microestrutura e comportamento em operação, com foco na diminuição do consumo e maximização dos lucros da empresa. Para tal, com o intuito de conhecer detalhadamente sua microestrutura e prever seu desempenho, foram realizadas análises de caracterização em laboratório e testes que simularam as condições de operação. Após os testes laboratoriais, os materiais selecionados foram testados em operação em forno elétrico a arco, buscando encontrar o melhor conjunto de materiais sob o ponto de vista de estabilidade do processo e custo de refratários. O cenário que apresentou melhores resultados em relação à performance e ao consumo específico foi a configuração A, onde foram utilizados os tijolos A, massa de soleira X, massa de reparo K e canal EBT P. Além disso, a substituição do tijolo C pelo tijolo A gerou uma redução de custo de 40%, e o conhecimento gerado com a caracterização do canal EBT proporcionou uma redução de 29,9% no preço desse item. / The steel industry, like other sectors of the industry, is seeking alternatives to reduce production costs and increase productivity. In electric steelworks, the main steel production costs can be divided, in a simplified way, between the cost of inputs and the cost of raw materials. Refractories are among the five largest costs in steel production in semi-integrated mills (mini-mills). However, detailed knowledge of the microstructure and behavior of these materials is still quite restricted to their manufacturers. Given the importance of the refractories in the production of steel, this study aimed to generate knowledge about their microstructure and behavior in operation, focusing on the reduction of consumption and maximization of profits. For that, in order to know in detail the microstructure and predict its performance, characterization analyzes and tests simulating the operating conditions were performed in the laboratory. After laboratory tests, the selected materials have been tested in operation in electric arc furnace, seeking to find the best set of materials from the point of view of stability of the process, and cost of refractories. The scenario that best results presented, in terms of performance and the specific consumption, was Configuration A, where bricks A, ramming mix X, repair mix K and EBT P were used. Moreover, the replacement of Brick B by brick A, generated a cost reduction of 40%, and the information gathered with the characterization of EBT, reduced the price of that item by 29.9%.

O pó de aciaria elétrica é um importante subproduto da indústria siderúrgica devido ao seu alto teor de zinco. Assim, tecnologias vêm sendo desenvolvidas visando seu aproveitamento, sendo o forno Waelz a mais difundida delas atualmente. No entanto, sua operação, por contar com um forno rotativo de grandes dimensões que abriga uma infinidade de fenômenos físico-químicos, apresenta difícil previsibilidade ab initio. Por essa razão, este trabalho faz uso de uma ferramenta avançada da termodinâmica computacional, destinada à modelagem de processos, chamada SimuSage, a fim de modelar o seu comportamento. Para a criação do modelo utilizou-se também uma base de dados termodinâmicos advinda do software FactSage e a plataforma de desenvolvimento Lazarus. Com base em dados e resultados operacionais da literatura, foi possível realizar simulações nos modos adiabático e isotérmico, comparando os resultados com os da prática industrial. Constatou-se uma grande capacidade do modelo de reproduzir os resultados da literatura, mesmo quando não há muita informação para aferição dos parâmetros, gerando boa concordância com a composição química relatada dos produtos Óxido Waelz e Escória Waelz. / The electric arc furnace dust is an important by-product of the steel industry due to its high content of zinc. Thus, technologies have been developed aiming for its use, and the Waelz Kiln is the most widespread of them today. However, counting on a very large rotary kiln that houses an infinity of physico-chemical phenomena, its operation is difficult to predict ab initio. For this reason, in order to model its behaviour this work uses an advanced tool of computational thermodynamics designed to process modelling, called SimuSage. To create the model, a thermodynamic database, provided by the FactSage software, as well as a development platform, Lazarus IDE, were also used. Based on operational data and results from de literature, it was possible to perform simulations on both adiabatic and isothermal modes comparing its results with the industrial practice. A great capability of the model to reproduce results from the literature was found, even when there is not much information for the parameters calibration, generating good agreement regarding the reported chemical composition for the products, Waelz Oxide and Waelz Slag.

A presente tese teve como objetivo fornecer subsídios teóricos e experimentais com vistas à reciclagem da carepa gerada em usinas mini-mills através de briquetes autorredutores para uso em FEA. Para atingir os objetivos vislumbrados, o trabalho foi estruturado em quatro principais tópicos: estudo de caracterização e de redutibilidade da carepa, escolha e caracterização do redutor para uso nos briquetes, elaboração e caracterização da mistura e ensaios de laboratório para avaliação do desempenho dos briquetes autorredutores. Os estudos de caracterização da carepa indicaram que este resíduo é constituído principalmente de wustita e se apresenta estratificada em três camadas: camada externa fina e porosa composta de hematita e magnetita, camada intermediária de wustita densa e camada interna de wustita porosa. A cinética de redução da carepa foi investigada em termobalança no intervalo de temperatura entre 830 e 1200°C com CO puro e mistura 90%CO-10%CO2. A energia de ativação aparente encontrada nesses ensaios variou de 71 a 80 kJ/mol e as observações microscópicas demonstraram que a redução da carepa segue um modelo topoquímico. A escolha do agente redutor para compor o briquete se deu através de ensaios de gaseificação ao CO2 e de autorredução em termobalança com três tipos de material carbonoso. A partir desses ensaios observou-se a seguinte ordem decrescente de reatividade e respectivas energias aparentes de ativação: Carvão Vegetal (Ea = 237 kJ/mol), Carvão Mineral (Ea = 214 kJ/mol) e Coque de Petróleo (Ea = 335 kJ/mol). Em virtude da maior reatividade do Carvão Vegetal frente aos demais, este redutor foi escolhido para uso nos briquetes. A mistura utilizada na confecção dos briquetes autorredutores teve como constituintes principais a carepa, os finos de carvão vegetal e aglomerantes (melaço e cal). Ensaios de caracterização em termobalança com atmosfera oxidante e aquecimento rápido indicaram uma perda de massa de cerca de 40%, referente às etapas de secagem, desvolatilização e autorredução da mistura. Nesses ensaios, observou-se elevadas taxas de perda de massa da mistura e uma notável complexidade dos fenômenos envolvidos, com reações simultâneas de combustão, autorredução e de oxidação do ferro, prevalecendo uma ou outra, dependendo da temperatura e da fração reagida de amostra. Através de procedimentos que buscaram reduzir a complexidade dos fenômenos envolvidos nas condições oxidantes, foi possível estimar que a energia de ativação aparente de autorredução está entre 62 e 69 kJ/mol. Os briquetes produzidos em escala industrial foram submetidos a ensaios isotérmicos e não-isotérmicos de alta temperatura. Tais ensaios buscaram determinar os gradientes térmicos no interior do briquete, a energia de ativação aparente e o desempenho cinético do aglomerado em condições de temperatura que se aproximam da prática industrial. A partir das constatações concernentes às taxas das reações químicas individuais (redução e gaseificação), às medidas do perfil de temperatura no interior dos aglomerados, à energia de ativação estimada para o briquete (93 kJ/mol) e ao modelo de redução encontrado nos ensaios de alta temperatura, acredita-se que tanto a cinética de redução da carepa como a transferência de calor sejam obstáculos limitantes da cinética global dos briquetes em estudo. Finalmente, os resultados de metalização obtidos nos testes de alta temperatura dão indícios da possibilidade de uso destes briquetes em FEA. / This dissertation aimed to provide theoretical and experimental basis for recycling of mill scale generated in mini-mill plants through the use of self-reducing briquettes in EAF. To reach these goals, the work was structured around four main topics: characterization and reducibility study of scale, choice and characterization of the reductant to use in briquettes, elaboration and characterization of the mixture and laboratory tests to performance evaluation of self-reducing briquettes. The characterization studies of mill scale have indicated that this waste is composed mainly of wustite and is stratified into three layers with different morphologies: fine porous external layer composed of hematite and magnetite, intermediate layer of dense wustite and inner layer of porous wustite. The kinetics of scale reduction was investigated in thermobalance in a temperature range from 830 to 1200°C with pure CO and a mixture of 90% CO and 10% CO2. The apparent activation energy obtained in these tests ranged from 71 to 80 kJ/mol and the microscopic observations showed that the mill scale reduction corresponds to a topochemical model. The choice of the reductant for composing the briquette was made through tests of gasification with CO2 and of self-reduction in thermobalance with three different carbonaceous materials. From the results, it was observed the following decreasing reactivity order and the related apparent activation energy: Charcoal (Ea = 237 kJ/mol), Mineral Coal (Ea = 214 kJ/mol) and Petroleum Coke (Ea = 335 kJ/mol). Due to the higher reactivity of Charcoal in relation to the others, this reducer was chosen to be used in the briquettes. The main constituents of the mixture used in the manufacture of self-reducing briquettes were scale, charcoal and binders (melasse and lime). The characterization tests in thermobalance with oxidizing athmosfere and rapid heating indicated a mass loss of about 40%, referring to the stages of drying, devolatilization and self-reduction of the mixture. During these tests, it were observed high rates of mixture loss mass and a remarkable complexity of the phenomena, with simultaneous combustion, self-reduction and iron oxidation reactions, where their importance changes according to temperature and fractional reaction of the sample. Through the procedures that aimed to reduce the complexity of the related phenomena in oxidant conditions, it was possible to estimate that the self-reduction apparent activation energy ranges between 62 to 69 kJ/mol. The briquettes produced in the industrial plant were submitted to isothermal and nonisothermal tests of high temperatures. Such tests aimed to determine the thermal gradients into the briquette, the apparent activation energy and kinetic performance of the agglomerate in temperature conditions similar to the ones used in industrial practice. Based on the findings concerning the individual rates of chemical reactions (reduction and gasification), the measures of the temperature profile inside the briquettes, the activation energy estimated (93 kJ/mol) and the reduction model found in high-temperature tests, it is assumed that both the kinetics of mill scale reduction and heat transfer limit the overall kinetic rates of these briquettes. Finally, the results of metallization obtained in the tests conducted at high temperatures indicate the possibility of using these briquettes into the EAF.

O setor siderúrgico, assim como os demais setores da indústria, vem buscando alternativas para a redução dos custos de produção e aumento de produtividade. Em aciarias elétricas, os principais custos de produção do aço podem ser divididos, de forma simplificada, entre o custo dos insumos e o custo das matérias primas. Os refratários estão entre os cinco maiores custos na produção do aço em usinas semi-integradas. Entretanto, o conhecimento detalhado da microestrutura e do comportamento desses materiais ainda é bastante restrito aos seus fabricantes. Tendo em vista a importância dos refratários na produção do aço, este trabalho teve como objetivo gerar conhecimento acerca de sua microestrutura e comportamento em operação, com foco na diminuição do consumo e maximização dos lucros da empresa. Para tal, com o intuito de conhecer detalhadamente sua microestrutura e prever seu desempenho, foram realizadas análises de caracterização em laboratório e testes que simularam as condições de operação. Após os testes laboratoriais, os materiais selecionados foram testados em operação em forno elétrico a arco, buscando encontrar o melhor conjunto de materiais sob o ponto de vista de estabilidade do processo e custo de refratários. O cenário que apresentou melhores resultados em relação à performance e ao consumo específico foi a configuração A, onde foram utilizados os tijolos A, massa de soleira X, massa de reparo K e canal EBT P. Além disso, a substituição do tijolo C pelo tijolo A gerou uma redução de custo de 40%, e o conhecimento gerado com a caracterização do canal EBT proporcionou uma redução de 29,9% no preço desse item. / The steel industry, like other sectors of the industry, is seeking alternatives to reduce production costs and increase productivity. In electric steelworks, the main steel production costs can be divided, in a simplified way, between the cost of inputs and the cost of raw materials. Refractories are among the five largest costs in steel production in semi-integrated mills (mini-mills). However, detailed knowledge of the microstructure and behavior of these materials is still quite restricted to their manufacturers. Given the importance of the refractories in the production of steel, this study aimed to generate knowledge about their microstructure and behavior in operation, focusing on the reduction of consumption and maximization of profits. For that, in order to know in detail the microstructure and predict its performance, characterization analyzes and tests simulating the operating conditions were performed in the laboratory. After laboratory tests, the selected materials have been tested in operation in electric arc furnace, seeking to find the best set of materials from the point of view of stability of the process, and cost of refractories. The scenario that best results presented, in terms of performance and the specific consumption, was Configuration A, where bricks A, ramming mix X, repair mix K and EBT P were used. Moreover, the replacement of Brick B by brick A, generated a cost reduction of 40%, and the information gathered with the characterization of EBT, reduced the price of that item by 29.9%.