Com a crescente ideia de sustentabilidade, surge a necessidade de utilização de recursos renováveis e reaproveitamento de resíduos gerados em processos industriais. Neste trabalho foi avaliada a utilização da cinza pesada oriunda da queima do carvão em usinas termoelétricas no desenvolvimento de um Cermet. O compósito Cinza-Ferro (Cz-10Fe) foi obtido por metalurgia do pó e é composto de cinza pesada moída com adição de 10% em massa de pó de ferro puro. A adição do ferro é justificada para melhoria das propriedades mecânicas do material cerâmico. O compósito foi aplicado como meio suporte para biofilme em filtro biológico percolador, no pós-tratamento de efluentes domésticos. Foram realizados estudos com os principais componentes da cinza, tais como a sílica (SiO2), em forma de pó de quartzo, e a alumina (Al2O3) na versão comercial para avaliação da interação dos mesmos com o ferro e avaliação de suas propriedades mecânicas sob influência da variação da temperatura de sinterização A cinza pesada, obtida na Usina Tractebel de Charqueadas, foi moída durante 2, 4 e 8 horas para determinação do tamanho de partícula ideal para o compósito. Após caracterização, foi selecionada cinza moída por 2 horas para a produção dos compósitos para aplicação. A aplicação se deu utilizando um protótipo no pós-tratamento de efluentes da Estação de Tratamento de Esgotos (ETE) da COMUSA visando a remoção de Demanda Química de Oxigênio (DQO). Obteve-se incremento na eficiência do processo, reduzindo a DQO do efluente final em média 9%, indicando a viabilidade de uso do protótipo no pós- tratamento de esgotos domésticos, com porosidade aproximada de 20%, obtidos na cinza moída por 2 horas e sinterizado com ferro, como meio suporte para biofilme em filtro biológico percolador. / With the crescent idea of sustainability, there is a necessity for the use of renewable resources and the reuse of waste generated in industrial processes. In this work the use of the coal bottom ash from thermoelectric plants was evaluated in the development of a Cermet. The composite Ash-Iron (Cz-10Fe) was obtained by powder metallurgy and is composed of ground heavy ash with addition of 10% by mass of pure iron powder. The addition of iron is justified to improve the mechanical properties of the ceramic material. The composite was applied as biofilm packing media in trickling filter in the post-treatment of domestic effluents. Studies with the main components of the ash, such as silica (SiO2), in the form of quartz powder, and alumina (Al2O3) in the commercial version were carried out to evaluate their interaction with iron and evaluation of their mechanical properties under influence of the sintering temperature variation The bottom ash obtained at Tractebel from Charqueadas was milling for 2, 4 and 8 hours to determine the ideal particle size for the composite. After characterization, milled ash for 2 hours was selected for the production of the composites for application. The application was done using a prototype in the post-treatment of effluents from the Wastewater Treatment Station (ETE) of COMUSA aiming at the removal of Chemical Oxygen Demand (COD). The efficiency of the process was obtained by reducing the COD of the final effluent by a mean of 9%, indicating the viability of the utilization the prototype in the post-treatment of domestic sewage, with approximate porosity of 20%, obtained in ground ash for 2 hours and sintered with iron powder, in biofilm packing media in trickling filter.

Ce travail de recherche s'inscrit dans une dynamique de valorisation des sous-produits industriels locaux dans l'industrie cimentière. Il porte essentiellement sur la possibilité d'utiliser la poudre de mâchefer de charbon produit par la SONICHAR au Niger pour élaborer des ciments composés. Après une caractérisation physico-chimique et environnementale de la poudre de mâchefer, nous avons déterminé sa réactivité pouzzolanique et son indice d'activité mécanique. Les résultats montrent que la poudre de mâchefer présente une pouzzolanicité dont la cinétique relativement lente ne démarre pas avant 14 jours. D'autre part, ce mâchefer peut être considéré comme une addition minérale du type Il selon la norme EN 206-1 avec un indice d'activité de 0,76. C'est pourquoi nous l'avons utilisé pour élaborer trois ciments composés de type CEM 11/A avec une classe de résistance de 42,5 lorsque le taux de substitution est de 10% et une classe de résistance de 32,5 lorsque Je taux de substitution est de 15% et 20%. Des mortiers normaux ont été élaborés à partir de ces ciments et caractérisés sur les plans physiques et mécaniques. La durabilité des mortiers a également été étudiée notamment du point de vue de la cinétique de carbonatation et de lixiviation en présence de nitrate d'ammonium. Il ressort en définitive que la poudre de mâchefer peut bien être incorporée comme addition dans l’élaboration de ciments composés. Les caractéristiques mécaniques à long terme (90 jours) et la durabilité des mortiers confectionnés à partir de ces ciments sont conservées lorsque le taux de substitution n'excède pas 10%. / This research is part of a process of valorization of local industrial by-products in the cement industry. lt focuses on the possibility f using coal bottom ash powder produced by SONICHAR in Niger as cement partial addition. After a physicochemical and environmental characterization of the coal bottom ash powder, we determined its pozzolanic reactivity and it mechanical activity index. The results show that the coal bottom ash powder presents a pozzolanicity whose relatively slow kinetics do ne start before 14 days. On the other hand, this coal bottom ash can be considered as a mineral addition of type 11 according to the standard EN 206-1 with an activity index of 0.76. This is why we used it to develop three CEM 11/A composite cements with a strength class of 42.5 when the substitution rate is 10% and a strength class of 32.5 when the rate of substitution is 15% and 20%. Normal mortars have been formulated with these cements and are characterized physically and mechanically. The durability of the mortars has also been studied, in particular from the point of view of the kinetics of carbonation and leaching in the presence of ammonium nitrate. Finally, it appears that the coal bottom ash powder may indeed be incorporated as an addition in the preparation of composite cements. The long-term mechanical characteristics (90 days) and the durability of the mortars made from these cements are preserved when the substitution rate does not exceed 10%.

Shredder fines are the materials with a particle size of less than 10 mm resulting from the shredding of vehicles and complex metal scrap from industries and municipalities. This waste is currently used as landfill construction material, but Stena Recycling wanted to know whether the bottom ash from the combustion of this waste could be useful to the cement industry, and whether it would be feasible to extract Cu and Zn from this ash. To determine this the shredder fines were combusted, and the generated bottom ash underwent chemical fractionation. The leachates from this were processed using MP-AES to obtain an elemental analysis of the ash. The uncombusted shredder fines had its moisture content and calorific value determined. The shredder fines had a moisture content of approximately 11%wt. Due to the heterogeneity of the shredder fines the calorific values varied significantly across the tested samples. The average value was 7.8 MJ/kg. The chemical fractionation showed that the elements in the ash are mostly insoluble in water and ammonium acetate, as the majority remained in the solid residue. This indicates that the ash is inert, and not susceptible to heavy metal leaching. The elemental analysis showed that there is a significant amount of Fe in the ash, with reasonable amounts of Cu and Zn. This project concluded that without additional processing the ash would not be suitable for the cement industry, and that there is potential for the recovery of Cu and Zn from the ash.

Bottom ash (BA), generated from the incineration of municipal solid waste (MSW), contains valuable elements which present a potential economic incentive to attempt recovery. The first study of this thesis investigated the physical, chemical, and mineralogical characterization of MSWI-BA samples through a number of experiments. To develop a proper physical characterization of the BA material, the sample was ground and subjected to particle size distribution, wet magnetic separation, and a float-sink test. As for the chemical and mineralogical characterization, the sample was subjected to XRD, XRF, SEM-EDX, and elemental composition analysis. Additionally, sequential chemical extraction and acid-leaching tests were conducted. The results from this section revealed that carrying out a combination of beneficiation processes using the MSWI-BA sample previously classified into the coarse, middle, and fine-size fractions could lead to better metal concentration yield and recovery optimization. The wet magnetic separation showed outstanding metallurgy indicators towards Fe, with enrichment ratios close to 2.0 and recovery values near to 80%. Metals such as Cu and Co were also enriched by 1.51 and 1.66, respectively, suggesting that the magnetic separation performance and enrichment are a function of the bound of multi-metallic oxides fractions. The 2.95 SG density test reached enrichment ratios higher than 2.0 in Fe, Cu, Co, and Ni in the coarse fraction of the BA fraction, which decreases when reducing the size fraction. When reducing the density cutoff, the results showed that the sink fraction yield increased as the medium density decreased, and the enrichment ratios of the minor elements (Mn, Co, Ni, Sn, and V) were similar across the different size fractions. Complementary information was obtained by the mineralogical characterization of the enriched streams from the physical concentration test, which explains the results obtained. The Cu speciation and mineral phases identified were copper oxide, copper sulfate, and cupric sulfite. While the main Fe-rich constituents existed in chemical forms of iron oxides, such as magnetite, hematite with substituted varieties, spinel group, and metallic inclusions. The enrichment ratios of Mn, Cr, Cu, and Ni obtained through magnetic separation can be explained by the presence of metallic inclusions, where these elements exhibit an affinity for the iron-bearing particles. The acid leaching test revealed that metals such as Fe, Mn, Co, Cu, and Zn can be efficiently leached using 1M HCl within 30 min of the reaction. The second part of this research study constituted the evaluation of the effect of the particle size reduction, which was performed to assess the intraparticle heterogeneity of MSWI BA. The evaluation consisted of particle size reductions by crushing and grinding for different residence times and then subjecting the sample to a sequence of physical concentration tests, such as particle size distribution, froth flotation, and wet magnetic separation. Additionally, the elemental composition after each test was determined through ICP-MS analysis to compare the particle size effect in the recovery and concentration of the valuable elements. The elemental composition results revealed that the comminution process promotes the interaction of Fe, Zn, and Cu, in the fine fraction, by generating more surface area. In contrast, the minor elements were not significantly enriched by reducing the size fraction, suggesting that the comminution process does not impact the mobility and redistribution of the elements in low concentrations. The froth flotation performed in this study showed that when using 0.338 g/ton diesel as a collector, adjusting and controlling the pH between 8.8 to 9.2 throughout the test, the organic matter content can be efficiently reduced in the BA sample from 14.73% to 4.25% when the sample has been previously ground for 30 min. Slight enrichment ratios were observed in the concentrate stream of the froth flotation, suggesting that these elements are associated with the organic matter in the BA sample. In contrast, the wet magnetic separation results revealed significant enrichment ratios of Fe, Mn, Co, and Ni after 10 min of grinding. / Master of Science / The Bottom Ash (BA) generated by the incineration of household solid waste has been identified as a promising source of valuable elements. However, a comprehensive understanding of the BA sample's properties is required in order to determine the most suitable mineral processing method to enrich the elements. The first study of this research consisted of evaluating BA ash's physical, chemical, and mineralogical properties in the BA sample. Following the characterization study, the effect of particle size, as a function of the grinding time, in the valuable elements' enrichment was evaluated. The results suggest that Ti, Fe, Cu, and Zn are the major and most valuable elements, while Mn, Co, Ni, Sb, and V are valuable elements in a minor concentration in the BA samples. Some elements, such as Ti, Sc, Co, Mn, Ni, Sn, and V, have been declared by the US Department of the Interior as critical minerals due to their economic importance and vulnerability to supply chain disruption. Although Fe and Cu are not considered critical minerals, their consumption in 2022 was 40 and 1.9 million metric tons, respectively. The development of national industry and enhancing the understanding of the alternative sources for the valuable elements present an opportunity to diversify local suppliers, pursue a vertical integration of the economic model, and reduce the third-party international vendors' dependency. Likewise, this research supports the aims to reduce the demand for primary natural resources and contribute to the circular economy model, in which energy, resources, and material are kept in a lifecycle while reducing landfilling disposal.

Résumé : Depuis le début du XXe siècle, la production de bétons secs représente une industrie importante pour le développement des infrastructures en bétons compactés au rouleau notamment pour la construction de barrages, de digues, de pavages, et les bétons moulés à sec pour la pré-fabrication de blocs de maçonnerie, de briques, de pierres de pavé, etc. La durabilité de celles-ci peut être améliorée en réduisant leur consommation de ciment Portland et de granulats naturels en utilisant, respectivement, des ajouts cimentaires et des matériaux granulaires alternatifs. D’ailleurs, beaucoup de sous-produits industriels et autres ajouts cimentaires alternatifs ne respectant pas les exigences pour le béton conventionnel ont été utilisés avec succès dans ce type de béton. Les cendres de biomasse sont des sous-produits prometteurs pour les applications de bétons secs. Ces cendres sont obtenues dans une centrale de cogénération de l’industrie des pâtes et papiers suite à la combustion de leurs boues de traitement des eaux usées, de leurs boues de désencrage, et autres résidus de bois. Les cendres volantes de biomasse (CVB) ont une finesse similaire à celle du ciment et elles possèdent aussi un potentiel de réactivité pouzzolanique. Elles peuvent donc remplacer une partie du ciment utilisé dans la formulation de bétons. Les cendres grossières de biomasse (CGB) ont une granulométrie voisine de celle d’un sable fin. Elles peuvent donc être valorisées en remplaçant une partie des granulats naturels utilisés dans les formulations de bétons. Bien que les propriétés physico-chimiques et les interactions cimentaires de celles-ci soient étudiées depuis le début des années 2000, très peu d’applications commerciales ou industrielles ont été développées. Ce projet de recherche vise l’étude et l'optimisation des CVB comme ajout cimentaire alternatif et des CGB comme granulats fins alternatifs dans la production de bétons compactés au rouleau (BCR) et à la paveuse (BCP) pour des applications de pavages industriels et dans la production de bétons moulés à sec (BMS) pour des applications de préfabrication de pierres de pavé. Pour chacune de ces applications, des formulations incorporant un taux de substitution jusqu'à 30% du ciment par des cendres volantes et jusqu’à 100% du sable par des cendres grossières ont été réalisées. Ces travaux d’optimisation ont été effectués avec des bétons à rap-port eau-liant de 0,32, 0,35 et 0,37. Les propriétés à l’état frais (maniabilité et consistance), à l’état durci (résistance à la compression, à la flexion et à la traction), et de durabilités (absorption à l’eau, vides perméables et résistivité électrique) jusqu'à 91 jours ont été mesurées pour tous les mélanges de béton. Le rapport eau-liant, la teneur en pâte et les taux de remplacement optimaux ont également été combinés et optimisés afin de valoriser un maximum de cendres de biomasse, volantes et grossières, dans une seule formulation. Les résultats des mélanges de BCR fabriqués en laboratoire avec 10% et 20% de CVB et combinés à 50% de CGB ont respectivement montré des maniabilités désirées et des résistances à la flexion supérieures aux limites prescrites par les devis techniques pour une utilisation pratique de 23% et 29%. Ces deux mélanges donc ont été sélectionnés pour évaluer leur comportement in situ à l’aide de la construction d'une dalle de stockage de 792 m² par 300 mm d'épaisseur à l'aide de pratiques courantes. Des carottes ont été prélevées dans la dalle à 28 et 308 jours. La résistance à la compression des noyaux à l'âge de 308 jours a atteint 33 et 30 MPa pour les deux mélanges testés, respectivement. Les BMS fabriqués avec 5%, 10%, ou 15% CVB et 25% de CGB peuvent atteindre un indice de compaction de 99% avec un travail de compaction inférieur à celui spécifié par les fabricants de pierre de pavés. L'utilisation des CVB et CGB entraîne une faible diminution de la résistance à la compression, mais présente des valeurs de perméabilité et d’absorption à l’eau très faibles et inférieures aux exigences requises les normes (près de 5%). Ces travaux de recherche présentent un débouché potentiel à la valorisation des cendres volantes et grossières de biomasse issues de l’industrie des pâtes et papiers dans les bétons secs comme ajout cimentaires ou granulats fins. Cette approche peut offrir une contribution significative pour la réduction des émissions de gaz à effet de serre associés à la production de ce type de béton et dans les gestions des matières résiduelles de l’industrie des pâtes et papiers. / Abstract : Since the early twentieth century, the production of dry concrete is an important industry for infrastructure development including the construction of dams, core dikes, and pavements using roller-compacted concrete, and precast masonry blocks, bricks, pavers using dry-cast concrete. The sustainability thereof can be improved by reducing its consumption of Portland cement and natural aggregates using cementitious supplementary cementitious materials and alternative granular materials, respectively. Moreover, many industrial by-products and other mineral additions not meeting the requirements for conventional concrete have been success-fully used in such concrete. The biomass ashes are promising supplementary materials for dry concrete applications. These ashes are produced in a cogeneration plant of the pulp and paper industry following the burn-ing of their wastewater treatment sludge, their de-inking sludge, and other wood residues. The biomass fly ash (BFA) have a similar finesse in the cement and they also have a potential poz-zolanic reactivity. They may therefore replace part of the cement used in concrete formula-tions. The biomass bottom ashes (BBA) have a particle size close to that of a fine sand. They can be use to replace a portion of the natural aggregates. Although the physicochemical proper-ties and interactions with cement have been studied since the early 2000s, very few commer-cial or industrial applications have been developed. This research project aims at studying and optimizing the BFA content as an alternative sup-plementary cementitious materials and the BBA content as an alternative fine aggregates in the production of roller-(RCC) and paver-compacted concrete (PCC) for industrial pavements and dry-cast concrete (DCC) for the manufacture of pavers. Formulations incorporating substitu-tion rates of cement up to 30% by BFA and of the sand up to 100% by BBA were evaluated for each of the mentioned applications. This optimization work was carried out with concrete water-to-binder ratio (w/b) of 0.32, 0.35 and 0.37. The fresh properties (workability and com-pactness), hardened properties (compressive strength, flexural strength and splitting-tensile strength) and transport properties (water absorption, permeable voids and electrical resistivity) up to 91 days were measured for all concrete mixtures. The optimal w/b, paste content and replacement rates were also combined and optimized in order to maximize the biomass fly and bottom ashes content, in a single formulation. The results of concrete mixtures made with 10% and 20% BFA with 50% BBA showed 23% and 29% higher flexural strength than the limits required for practical use of RCC, respective-ly. These two RCC mixtures were selected for the assessment of in situ behaviors through the construction of a storage slab of 792 m² per 300 mm thick using standard practices. Core sam-ples were cut from the slabs at age of 28 and 308 days for follow-up of the concrete behavior with time. The compressive strength of the cores at an age of 308 days reached 33 and 30 MPa for the two tested mixtures, respectively. The DCC mixtures made with 5%, 10%, or 15% BFA and 25% of BBA can reach a compact-ness index of 99% with a compaction work lower than specified by the Standards. The use of the BFA and BBA lead to small decrease of the compressive strength, however they can result in very low permeability and water absorption values lower than required by the specifications (close to 5%). This research presents a potential market for recycling biomass fly and bottom ashes from the pulp and paper industry in dry concrete as alternative supplementary cementitious materials or fine aggregates. This approach can provide a significant contribution to reduce greenhouse gas emissions associated with the production of this type of concrete and with the managements of by-products from the pulp and paper industry.

Μεγάλο τμήμα της παραγόμενης ενέργειας στην Ελλάδα προέρχεται από την καύση λιγνίτη στην Βόρεια (Δυτική Μακεδονία) και Νότια (Πελοπόννησος) Ελλάδα. Η καύση του λιγνίτη έχει ως αποτέλεσμα την παραγωγή μεγάλων ποσοτήτων στερεών παραπροϊόντων, όπως η ιπτάμενη τέφρα (ΙΤ) και η τέφρα πυθμένα (ΤΠ), των οποίων η συνολική παραγωγή ανέρχεται σήμερα σε 14Mt ετησίως. Η ποσότητα των παραπροϊόντων αυτών αναμένεται να αυξηθεί τα επόμενα χρόνια εξ’ αιτίας της συνεχώς χαμηλότερης ποιότητας λιγνίτη που χρησιμοποιείται (χαμηλότερη θερμογόνος δύναμη). Ένα τμήμα της παραγόμενης ΙΤ (10-12%) στην Ελλάδα αξιοποιείται ως πρώτη ύλη στη παραγωγή τσιμέντου, ενώ η ΤΠ δεν απορροφάται μέχρι σήμερα από καμία εφαρμογή, κυρίως λόγω του υψηλού ποσοστού άνθρακα που περιέχει. Το αντικείμενο της παρούσας διατριβής είναι η αξιοποίηση, πρωτίστως, της ΤΠ και, μετέπειτα, της ΙΤ ως πρώτες ύλες στην παραγωγή τεχνητών ελαφροαδρανών για χρήση τους στην παραγωγή ελαφροσκυροδέματος. Για την παραγωγή των τεχνητών ελαφροαδρανών εφαρμόστηκε η διεργασία της πυροσυσσωμάτωσης σε σχάρα (grate sintering) έπειτα από σφαιροποίηση μιγμάτων των δύο τεφρών. Πραγματοποιήθηκε διερεύνηση των φυσικοχημικών χαρακτηριστικών των λιγνιτικών τεφρών (Κεφάλαιο 2) με σκοπό τον προσδιορισμό και την κατανόηση των χαρακτηριστικών τους, τα οποία αναμένεται να έχουν σημαντική επίδραση στην εφαρμογή της διεργασίας και στην ποιότητα του παραγόμενου προϊόντος. Επιπλέον, γίνεται αναλυτική αναφορά στα βασικά χαρακτηριστικά των διεργασιών σφαιροποίησης και πυροσυσσωμάτωσης (Κεφάλαιο 3). Για την εφαρμογή της επιλεγμένης διεργασίας παραγωγής τεχνητών ελαφροαδρανών πραγματοποιήθηκε σχεδιασμός μιγμάτων με διαφορετικές αναλογίες ΤΠ και ΙΤ (Κεφάλαιο 4). Ο περιεχόμενος άνθρακας της ΤΠ αποτελεί το καύσιμο της διεργασίας πυροσυσσωμάτωσης, ενώ η υψηλή περιεχόμενη υγρασία της ΤΠ αξιοποιείται ως το κύριο συνδετικό υλικό κατά την διάρκεια σφαιροποίησης για τον σχηματισμό σφαιριδίων. Οι διαφορετικές αναλογίες ΤΠ και ΙΤ αντιστοιχούν σε διαφορετικό ποσοστό στερεού καυσίμου στο μίγμα (προκύπτει από τις διαφορετικές vi αναλογίες), μία παράμετρος η οποία έχει επίδραση στην ολοκλήρωση της πυροσυσσωμάτωσης και στην ποιότητα του παραγόμενου (ελαφροαδρανούς) προϊόντος. Η πυροσυσσωμάτωση ολοκληρώθηκε με επιτυχία με ελάχιστο ποσοστό στερεού καυσίμου (περιεχόμενο άνθρακα ΤΠ) 6.5%κβ (Κεφάλαιο 5). Πραγματοποιήθηκε φυσικοχημικός χαρακτηρισμός όλων των προϊόντων της πυροσυσσωμάτωσης των μιγμάτων λιγνιτικών τεφρών της Μεγαλόπολης, και διαπιστώθηκε ότι το ποσοστό περιεχόμενου άνθρακα της ΤΠ είναι μια πολύ σημαντική παράμετρος για την παραγωγή ελαφροαδρανών υλικών. Ο σχηματισμός πορώδους δομής στο εσωτερικό των πυροσυσσωματωμένων πελλετών, στην οποία οφείλεται και το χαμηλό βάρος των παραγόμενων αδρανών, προκαλείται από την ταυτόχρονη εξέλιξη δύο διεργασιών: α) την παραγωγή αερίων σε υψηλές θερμοκρασίες και β) τον σχηματισμό ρευστής φάσης στην εξωτερική επιφάνεια της πελλέτας στο ίδιο χρονικό διάστημα (Κεφάλαιο 6). Οι αντοχές των πυροσυσσωματωμένων πελλετών οφείλονται σε αντιδράσεις και στον σχηματισμό νέων φάσεων είτε στερεών μέσω διάχυσης είτε ρευστών που προέρχονται από επιτήξεις στα όρια των κόκκων. Στην συνέχεια τα παραγόμενα ελαφροαδρανή χρησιμοποιήθηκαν για την παραγωγή δοκιμίων θερμομονωτικού και δομικού ελαφροσκυροδέματος και πραγματοποιήθηκε έλεγχος των θερμικών και μηχανικών τους ιδιοτήτων, αντίστοιχα (Κεφάλαιο 7). Τα αποτελέσματα δείχνουν ότι τα τεχνητά ελαφροαδρανή μπορούν να χρησιμοποιηθούν για την παραγωγή θερμομονωτικού και δομικού ελαφροσκυροδέματος. Η επιτυχής παραγωγή τεχνητών ελαφροαδρανών από μίγματα λιγνιτικών τεφρών Μεγαλόπολης αποτέλεσε και την βάση για δοκιμές πυροσυσσωμάτωσης των παραπροϊόντων αυτών με άλλα στερεά βιομηχανικά παραπροϊόντα όπως η ερυθρά ιλύς (ΕΙ), η οποία παράγεται από την επεξεργασία βωξίτη προς παραγωγή αλουμινίου (Κεφάλαιο 8). Για την διαπίστωση της συνεργασίας των δύο διαφορετικών παραπροϊόντων πραγματοποιήθηκε προσθήκη μέχρι και 30%κβ ΕΙ σε μίγματα λιγνιτικών τεφρών. Πραγματοποιήθηκε φυσικοχημική διερεύνηση των προϊόντων της πυροσυσσωμάτωσης και χρήση τους στην παραγωγή δοκιμίων σκυροδέματος. Τα αποτελέσματα δείχνουν ότι η αύξηση της προστιθέμενης ΕΙ στο μίγμα λιγνιτικών vii τεφρών της Μεγαλόπολης επιφέρει αύξηση στο βάρος των παραγόμενων αδρανών, ενώ μπορούν να χαρακτηριστούν ελαφροαδρανή τα προϊόντα πυροσυσσωμάτωσης μιγμάτων μέχρι και 20%κβ προσθήκης ΕΙ. Τα αποτελέσματα των μετρήσεων των μηχανικών αντοχών των δοκιμίων σκυροδέματος δείχνουν ότι η ΕΙ επιφέρει αύξηση στις αποκτώμενες αντοχές σε ποσοστό προσθήκης μέχρι και 15%κβ. Η εφαρμογή που προτείνεται σε αυτή την διατριβή για την παραγωγή τεχνητών ελαφροαδρανών υλικών από τα στερεά λιγνιτικά παραπροϊόντα του ΑΗΣ Μεγαλόπολης αποτελεί την πρώτη πρόταση για αξιοποίηση της ΤΠ στην Ελλάδα. Η πυροσυσσωμάτωση μιγμάτων των λιγνιτικών τεφρών μπορεί να οδηγήσει στην παραγωγή τεχνητών ελαφροαδρανών για χρήση τους στο δομικό και θερμομονωτικό ελαφροσκυρόδεμα ενώ ο περιεχόμενος άνθρακας της ΤΠ, ο οποίος αξιοποιείται ως το καύσιμο διεργασίας παραγωγής, αποτελεί σημαντική παράμετρο για την ποιότητα των τεχνητών ελαφροαδρανών. Επιπλέον, οι λιγνιτικές τέφρες της Μεγαλόπολης μπορούν να συνεργαστούν με άλλα στερεά βιομηχανικά παραπροϊόντα όπως η ΕΙ για την παραγωγή τεχνητών ελαφροαδρανών διαφορετικής ποιότητας. Επίσης, η συγκεκριμένη πρόταση αφορά στην μαζική αξιοποίηση της ΤΠ και πιθανή εφαρμογή έχει την δυνατότητα να απορροφήσει το μεγαλύτερο τμήμα του παραγόμενου αυτού παραπροϊόντος. / Large part of energy demand in Greece is covered by lignite combustion in West Macedonia and Peloponnesus. Lignite combustion results in production of, approximately, 14Mt/year of solid byproducts, such as fly ash (FA) and bottom ash (BA). The quantity of these byproducts is going to be increased in future because of the low quality of available lignite (lower calorific value). Part of FA (10-12%) produced in Greece is utilized as raw material in cement production while there is no application of BA, mainly because of its high carbon content. This study investigates a new method for utilization of BA, primarily, and FA, afterwards, as raw materials in the production of lightweight aggregates and further utilization of produced aggregates in lightweight aggregate concrete. A two stage process, pelletization and sintering, is applied in BA and FA mixtures. Physical and chemical analyses of Megalopolis lignite ashes are performed (Chapter 2) in purpose of characterization of process raw materials. Furthermore, fundamental theory of pelletization and grate sintering is presented (Chapter 3) in purpose of better understanding of process details. Mixtures of different BA/FA ratio are prepared for sintering tests (Chapter 4). Carbon contained in BA is utilized as the fuel of the process, while high water content of BA is utilized as the primary binding material during pelletization in purpose of pellets formation. Different BA/FA ratios represent different solid fuel percentages in sintering mixtures. This is an important parameter, which strongly affects the completion of the process and the quality of product. Successful completion of sintering process is achieved with minimum solid fuel content (BA carbon) 6.5wt% in mixture (Chapter 5). Physical and chemical characterization is performed for products of all different sintering mixtures. The results show that BA carbon content is an important parameter for the production of lightweight aggregates. Porous structure formation inside the sintered pellets, which is responsible for aggregates low weight, is caused by simultaneous development of two different processes: a) production of gases in high temperatures and, b) liquid (glassy) phase formation in the outer part of pellets in the same time period (Chapter 6). ix Formation of either solid state bonds, through diffusion, and/or glassy phase bonds at the points of particles mutual contact are responsible for pellet strength. Lightweight aggregates produced are used in the production of insulating and structural lightweight aggregate concrete specimens and thermal and mechanical tests are performed, respectively. According to tests results artificial lightweight aggregates can be used for insulating and structural purposes. The successful experimental results from the utilization of lignite solid byproducts in the production of LWA offered new opportunities for collaboration of these byproducts with other industrial solid residues, such as red mud (RM) which is produced during bauxite treatment for aluminum production (Chapter 8). In purpose of investigation of collaboration of these different byproducts sintering mixtures are prepared with low RM addition, up to 30wt%, in lignite ashes mixtures. Physical and chemical characterization is performed for products of all sintering mixtures and they are used for production of concrete specimens. Results show that increase of RM addition brings increase in aggregates weight, while aggregates formed by RM addition up to 20wt% can be considered as lightweight ones. The results of mechanical strength tests in concrete specimens show that RM addition up to 15wt% brings increase in aggregates strength. This is the first proposed method for utilization of lignite BA in Greece in the production of lightweight aggregates. Sintering of mixtures of lignite ashes results to the production of lightweight aggregates and the produced aggregates can be used for insulating and structural lightweight aggregate concrete. BA carbon content, which is utilized as the fuel of the process, is an important parameter for lightweight aggregate production and porous structure formation. Furthermore, Megalopolis lignite ashes can be treated in collaboration with other industrial solid byproducts, such as RM for the production of lightweight aggregates of different quality. Finally, the proposed method targets to massive utilization of BA produced in Megalopolis power station.

Certain types of waste, e.g. bottom ash originating from municipal solid waste incineration (MSWI bottom ash) can be used as road construction materials. A potential problem is the possibility of substances leaching out of the road and spreading in the surrounding groundwater. The aim of this master’s thesis is to conclude whether hydrogeological type settings can be employed to, based on local conditions, provide an estimate of the probable spreading of these substances in the surrounding groundwater, and whether certain types of soils can be identified as being less suitable for the localization of a MSWI bottom ash road. A hydrogeological type setting is defined as a mappable unit with similar hydrogeological properties. An advantage of this approach would be that mainly existing maps and surveys could form the basis for the assessment. The work has been performed by placing a hypothetical road construction in different hydrogeological type settings. The expected patterns of spreading has then been evaluated using theoretical reasoning and analytical and numerical models. The method can be used. In the report various type settings are defined. In several cases further information will be required to render possible a more exact estimate of the spreading. By locating the road on less permeable soils to reduce the local spreading of substances in groundwater, a greater proportion of the water will be drained as surface water. Thus it becomes important to take into account surface water transport aswell. In the report a procedure to estimate the maximum concentrations in groundwater at locations situated downstream the road is presented. This estimate could be used as basis for a more balanced valuation of appropriateness, e.g. by relating the estimated concentrations to background values. / Vissa typer av avfall, exempelvis slaggrus (sorterad bottenaska från avfallsförbränning), kan användas som vägbyggnadsmaterial. Ett potentiellt problem är möjligheten att ämnen lakas ut ur vägen och sprids i omgivande grundvatten. Syftet med detta examensarbete är att avgöra om hydrogeologiska typmiljöer kan användas för att, utifrån omgivningens förutsättningar, ge en bild av hur den vidare spridningen av dessa ämnen i omgivande grundvatten sannolikt ser ut, och om vissa typer av mark kan pekas ut som mindre lämpade för lokalisering av en slaggrusväg. En hydrogeologisk typmiljö definieras som ett område möjligt att avgränsa med avseende på karakteristiska hydrogeologiska förhållanden. En fördel med angreppssättet skulle vara att underlagsmaterialet till bedömningen då kan utgöras av i huvudsak befintligt kartmaterial. Studien har utförts genom att en hypotetisk vägkonstruktion placerats in i olika hydrogeologiska typmiljöer. De troliga spridningsscenarierna har sedan utvärderats genom teoretiska resonemang, samt genom användande av analytiska och numeriska modeller. Metodiken går att använda och i rapporten definieras olika typmiljöer. I flera fall kommer platsspecifik kunskap behöva inhämtas för en närmare beskrivning av spridningsbilden. Genom placering av vägen på tätare mark för att minska lokal spridning av ämnen i grundvatten kommer en större andel av vattnet att avledas som ytvatten. Därmed blir det viktigt att även inhämta kunskap om transport med ytvatten. I rapporten presenteras också en metod för uppskattning av maximala halter i grundvatten nedströms en väg. Denna metod kan användas som underlag för en mer nyanserad värdering av lämplighet, genom att de uppskattade halterna relateras till bakgrundsvärden eller lämpliga riktvärden.

Incineration is a mainstream strategy for solid waste management in Sweden and all over the world. Improved knowledge and understanding about the distribution of trace elements (in ashes) during incineration, and how trace element partitioning respond to the changes in waste composition, are important in terms of combustion process optimization and plant efficiency. Moreover, determination of chemical association of trace elements in ashes are vital for avoiding environmental concerns and to promote possible reuse. In this study, partitioning of trace elements in ashes during incineration as function of input waste fuel and incineration technology was investigated. Further, chemical association of trace elements in resulting ashes was studied. An evaluation was also performed about feasibility of metal extraction from sulfidic mining waste and flotation tailings. Moreover, green liquor dreg (GLD) was tested with respect to stabilization of metals within the sulfidic mining waste. Findings showed that the total input of trace elements and chlorine affects the partitioning and increasing chlorine in the input waste caused increase in transfer of trace elements to fly ash especially for lead and zinc. Vaporization, condensation on fly ash particles and adsorption mechanisms play an important role for metal distribution. Firing mixed waste, especially biofuel mix, in grate or fluidized (CFB) boilers caused increased transfer into fly ash for almost all trace elements particularly lead and zinc. Possible reasons might be either an increased input concentration of respective element in the waste fuel, or a change in volatilization behavior due to the addition of certain waste fractions. Chemical association study for fly ashes indicated that overall, Cd, Pb, Zn, Cu and Sb are presenting major risk in most of the fly ashes, while in bottom ashes, most of elements are associated with stable fraction. Further, fuel type affects the association of elements in ashes. Chemical leaching of mining waste materials showed that sulfuric acid (under different conditions) is the best reagent to recover zinc and copper from sulfidic mining waste and also copper from flotation tailings. GLD indicates potential for metal stabilization in mining waste by reducing the metal mobility. Extraction methods could be applied to treat mining waste in order to meet the regulatory level at a specific mining site.Similarly stabilization/solidification  methods might be applied after leaching for recovery of metals.

Submitted by Nadir Basilio (nadirsb@uninove.br) on 2016-06-20T14:26:30Z No. of bitstreams: 1 Mario Roberto Dos Santos.pdf: 2805393 bytes, checksum: 05385968aee97107c3fb2c3af54f225c (MD5) / Made available in DSpace on 2016-06-20T14:26:30Z (GMT). No. of bitstreams: 1 Mario Roberto Dos Santos.pdf: 2805393 bytes, checksum: 05385968aee97107c3fb2c3af54f225c (MD5) Previous issue date: 2015-08-21 / The aim of this study was to evaluate the eco-efficiency of the transformation of industrial waste in potential profitable co-products, as a business approach to reducing environmental impacts within the supply chain. The paper was based on to the following research question: How to measure the eco-efficiency of companies that value their industrial waste to allocate or offer them as alternative raw material for other industries? In this context, bottom ash resulting from the coal combustion in power plants was evaluated as a alternative raw material replacing sand in the production of ceramic materials and clinker in Portland cement industry, as an approach to eco-efficiency in power plants. The methodological procedures have been carried out in three phases: data collection through interviews; secondary data collection in thesis and periodical articles for the Life Cycle Assessment [LCA] preparation and the data evaluation. Pollutant emissions to atmosphere, water and soil were measured in numerical terms, relating to the production process of electric power and its waste, focused on bottom ash. All pollutants emissions to atmosphere, water and soil in numerical terms relating to the production process of sand and clinker were also measured. The evaluation has been carried out following the ABNT NBR ISO 14045 standard. The inventory calculation was based on primary data collected directly in the studied company and secondary data collected from the literature and regulatory agencies and analyzed by the software SimaPro. Within the limits of this research, it can be inferred that the eco-efficiency measure is carried out in two steps: 1) assessment of environmental impacts through research of the environmental aspects involved in the production process from the extraction of raw materials to the final disposal of waste and compare them to the production process to include the use of such waste. For this evaluation it was essential to measure LCA of waste (or wastes) to be evaluate and to compare the two processes (using and without using residue) so you can check what the major impacts are. Calculate the eco-efficiency of the process; 2) survey the probable cost’s uses of this waste in other production processes so that you can check for a monetary threshold that can afford possible valuation resulting from the new operations additions to the delivery of waste to another industrial sector. Based on these two phases it was possible to established eco-efficiency of the project, from both environmentally and economic perspectives. This research used the ReCiPe endpoint score method that presented the following results: a) Eco-efficiency of the generation of bottom ash for use in the ceramic industry compared with the generation of bottom ash by thermal plant and replacing the sand by the bottom ash in the production of ceramic tiles, thermal plant eco-efficiency spend 0.2% lower to 0.97% higher; b) Eco-efficiency of generation of bottom ash for use in cement industry compared with the generation of bottom ash by thermal plant and replacing the clinker by between 15-50%, have eco-efficiency values ranging from 2.4% to 11.5%. The use of bottom ash total replacement scenario of industrial sand in the production of ceramic tiles can use 91% of the amount spent on the acquisition of sand to buy the bottom ash. The use of bottom ash in the partial replacement scenario clinker in Portland cement production is that 91.4% of the clinker value can be used in the purchase of bottom ash. We can infer that it is possible to measure the eco-efficiency by measuring the environmental impacts through the ACV of the waste and, together, economically test the feasibility of their use. / O objetivo desta pesquisa foi avaliar a ecoeficiência da transformação de resíduos industriais em potenciais coprodutos rentáveis, como uma abordagem empresarial para a redução dos impactos ambientais dentro de uma cadeia de suprimentos. Este trabalho teve como referência a seguinte questão de pesquisa: Como medir a ecoeficiência das empresas que valorizam seus resíduos sólidos industriais ao destiná-los como matéria-prima alternativa para outros setores industriais? Nesse contexto, foi avaliada a valorização de cinzas pesadas, provenientes da combustão de carvão mineral em usinas termelétricas, como matéria-prima alternativa em substituição da areia na produção de materiais cerâmicos e também na substituição do clínquer na indústria de cimento Portland, como uma abordagem de ecoeficiência em termelétricas. Os procedimentos metodológicos foram realizados em três fases: levantamento dos dados por meio de questionários e entrevistas; levantamento de dados secundários em teses e artigos de periódicos para elaboração da Avaliação do Ciclo de Vida [ACV]; e a avaliação dos dados. Foram dimensionadas as emissões de poluentes para atmosfera, água e solo em termos numéricos relativos ao processo produtivo de energia elétrica e seus resíduos, com o foco nas cinzas pesadas. Foram dimensionadas também todas as emissões de poluentes para atmosfera, água e solo em termos numéricos relativos ao processo produtivo da areia e do clínquer. A avaliação foi realizada segundo a norma ABNT NBR ISO 14045. O cálculo do inventário foi baseado em dados primários levantados diretamente na empresa estudada e os dados secundários coletados na literatura e nas agências reguladoras e analisados pelo software SimaPro. No limite desta pesquisa, pode-se inferir que a medida de ecoeficiência seja realizada em duas etapas: 1) avaliação dos impactos ambientais por meio da pesquisa dos aspectos ambientais envolvidos no processo produtivo desde a extração das matérias-primas até a disposição final dos resíduos e sua comparação com o processo produtivo com a inclusão do uso desses resíduos. Para essa avaliação, é fundamental dimensionar a ACV do resíduo (ou dos resíduos) a ser valorizado e comparar os dois processos (sem uso e com do resíduo) para que se possa verificar quais são os maiores impactos. Calcular o valor da ecoeficiência do processo; 2) levantamento dos prováveis custos do uso desses resíduos em outros processos produtivos para que se possa verificar se há uma margem monetária que possa arcar com possíveis valores decorrentes do acréscimo de novas operações até a entrega do resíduo para outro setor industrial. Baseado nessas duas etapas, foi possível estabelecer a ecoeficiência, tanto ambiental quanto econômica do projeto. Esta pesquisa utilizou o método ReCiPe endpoint H pontuação única, que apresentou os seguintes resultados: a) Ecoeficiência da geração de cinzas pesadas para uso na indústria de revestimentos cerâmicos comparada com a geração de cinzas pela termelétrica e a substituição da areia pelas cinzas pesadas na produção de revestimentos cerâmicos, a ecoeficiência da termelétrica passaria de 0,2% inferior para 0,97% superior; b) Ecoeficiência da geração de cinzas pesadas para uso na indústria de cimento comparada com a geração de cinzas pela termelétrica e a substituição do clínquer por cinzas pesadas em quantidades de massa entre 15-50%, têm-se valores de ecoeficiência variando de 2,4% a 11,5%. O uso das cinzas pesadas no cenário de substituição total da areia industrial na produção de revestimentos cerâmicos poderá usar 91% do valor gasto na aquisição de areia para comprar as cinzas pesadas. No uso das cinzas pesadas no cenário de substituição parcial do clínquer na produção de cimento Portland tem-se que 91,4% do valor do clínquer poderá ser utilizado na compra das cinzas pesadas. Pode-se inferir que é possível medir a ecoeficiência medindo-se os impactos ambientais, por meio da ACV do resíduo e, em conjunto, verificar economicamente a viabilidade do seu uso.

Cement-based concrete is one of the main construction materials that is widely used for many construction applications due to its strength, durability, reflectivity, and versatility. However, it is acknowledged that production of cement as a primary material of concrete releases 1.8 Gt carbon dioxide (CO2) into the environment. It is estimated that one ton of cement production releases one ton of CO2 to the atmosphere. That is why, this work aims to create a concrete that could be an alternative to cement-based concrete. Geopolymer concrete (GPC) is an eco-friendly construction material and an alternative to conventional concrete that is produced by reacting aluminate and silicate bearing constituents with a caustic activator (i.e. sodium-based or potassium-based). Both potassium and sodium have been considered as generally safe intergradient by the FDA, based upon the observance of several good manufacturing practice conditions of use. Theses activators are used in various application including concrete, food, as a stabilizer, and as a thickening agent. Moreover, these activators are also used in making soap, as an electrolyte in alkaline batteries and in electroplating, lithography, and paint and varnish removers. Medically, these activators are widely used in the wet mount preparation of various clinical specimens for microscopic visualization of fungi and fungal elements in skin, hair, nails, and even vaginal secretions, Currently, it was determined that these activators solution were found to be a safe and effective treatment of plane warts. Despite the developments in the studies relating to GPC made by various precursors such as fly-ash and slag in the literatures, the use of GPC made by fly-ash and bottom-ash has not been overly researched. In this study, attempts have been made to produce a unique mix proportion for Potassium-based GPC made by fly-ash and bottom-ash and investigate various mechanical properties of this type of GPC including elastic modulus, freeze-thaw resistance, heavy metal leach-ability and corrosion in both laboratory and real environmental conditions using Non-Destructive Tests (NDT)s. / Graduate / 2021-12-15