Neste trabalho, vidros contendo um resíduo industrial denominado lama vermelha, foram desenvolvidos e caracterizados. Foi utilizada a quantidade mínima de 60% em massa de lama vermelha na produção dos vidros para promover a utilização desse resíduo. De acordo com os resultados de difração de raios X obtidos, observa-se que é possível produzir materiais a partir da lama vermelha com fases amorfas consideráveis, embora fases cristalinas referentes ao Fe originário do resíduo estejam presentes. O material denominado 60L40S, o qual possui 60% em massa de lama vermelha na sua composição nominal, apresentou as melhores propriedades dentre as composições estudadas, porém apresentou também alta temperatura de fusão. Ajustes na composição desse material foram realizados buscando diminuir essa temperatura. Os resultados mostram que os ajustes foram satisfatórios no desempenho de diminuir a temperatura de fusão, porém perdas na propriedade química desse material foram observadas. Elementos comumente encontrados na composição química de rejeitos nucleares foram adicionados aos vidros produzidos neste trabalho visando estudar os efeitos dessa adição nas propriedades químicas e térmicas desses materiais. Foi observado que é possível adicionar até 15% em massa de elementos simuladores aos materiais produzidos e essa adição promove a diminuição da temperatura de fusão. Acima de 15% em massa os elementos adicionados se precipitam na estrutura do material. Foi observado que, embora haja perdas na durabilidade química do material 60L40S após a adição dos elementos simuladores, esse material, quando em contato com água, mantém os elementos simuladores confinados em sua estrutura. Esse resultado é promissor, pois sugere que o material 60L40S é capaz de imobilizar em sua estrutura elementos provenientes de rejeitos nucleares. / Glasses based on red mud, a residual material from bauxite processing, were developed and characterized in this work. In order to promote its use, a minimum 60 wt% of red mud was used in the production of the glasses. According to XRD results, materials containing considerable amorphous phases were produced when using red mud as raw material. These amorphous phases were observed even though crystalline phases associated to Fe coming from the red mud itself were present. The material denominated 60L40S, which has a nominal composition of 60 wt% red mud showed the best properties comparing with the others compositions studied. However, these materials presented a high melting temperature. Changes in the composition of this material were made with the objective of lowering this temperature. Results indicated that the changes made to the material were successful in the reduction of the melting temperature. However, a reduction in the chemical properties of the resulting material was observed. Elements usually found in the chemical composition of nuclear wastes were added to the glasses produced. It was done with the objective of determining the effect of these elements on the chemical and physical properties of the red mud based glasses obtained. It was found that it was possible to add up to 15 wt% of these elements to the materials produced. The addition of these simulants materials promoted a reduction in the melting temperature of the resulting material. Above 15 wt%, the added elements precipitate in the structure of the resulting material. Even though the reduction in the chemical durability of the 60L40S material when simulant elements were added, it was observed that this material contained the simulant elements confined in its structure when in contact with water. This is a promising result, since it indicates that the 60L40S has the potential to immobilize elements from nuclear wastes.

A lama vermelha é o resíduo gerado pela Indústria do Alumínio. Assim como outros resíduos industriais apresenta características complexas com inúmeras dificuldades de manipulação, além de ser um material perigoso pela sua baixa granulometria e alcalinidade. É um resíduo com potencial poluidor alto, agravado pela forma de disposição vulnerável geralmente adotada, sendo esta a disposição do resíduo em lagoas projetadas para esta finalidade. O estudo e desenvolvimento de alternativas sustentáveis para a utilização da lama vermelha devidamente tratada como matérias-primas de outros processos são tendências importantes e necessárias no contexto mundial de preservação do meio ambiente. O objetivo deste estudo é compreender o comportamento da lama vermelha sob a influência de diferentes temperaturas de tratamento térmico. Baseados nos efeitos de redução de área e transformações de fases, característicos dos processos térmicos, adotou-se um foco de análise voltado para a redução pH e dos íons livres. A identificação dos pHs adequados de análise da concentração de íons solúveis foi feita com base nas curvas de mobilidade eletroforética e condutividade. Os resultados obtidos para as amostras calcinadas mostraram queda do pH inicial das dispersões e da concentração dos íons solubilizados. Esse efeito pode ser atribuído a redução de área e a incorporação de íons à estrutura, o que assegura ao resíduo menor reatividade. / Red mud is the waste generated by Aluminium Industry, like other industrial wastes, has complex features with several difficulties in handling, as well as being a hazardous material because of its low particle size, alkalinity and high amount generated. It is a waste with high pollution potential, compounded by the vulnerability of the disposition generally adopted, usually in lagoons designed for this purpose. The study and development of sustainable alternatives for the use of properly treated red mud, as raw material of other processes, are important tendencies and necessaries in the global context of environmental preservation. However, this work deals the thermal treatment as method to modify the characteristics of the waste, suggesting the reduction of alkalinity with the lower leaching of alkaline ions. This approach can be a discarding alternative most reliable and safe for the environment. The objective of this study is understand the red muds behavior using thermal treatment. Based on the reduction effects of the area and phase transformations characteristic of thermal process, the analysis was taken observing the reduction of free ions and pH. Identification of correct pH of analyse of soluble ions concentration was based at mobility electrophoretic and conductivity graphics. The results of calcined samples showed reduction of initial pH and the concentration of soluble ions. This effect could be assigned to the area reduction and ions incorporation at structure, which ensures the residue lower reactivity.

In this study, effects of changes in various parameters of the Bayer process on the amount of &ldquo / red mud&rdquo / , which has many environmental drawbacks, were examined in accordance with the principles of &ldquo / sustainable development&rdquo / . The production process of SeydiSehir Aluminum Plant is modeled as a case study. First a steady-state mass balance calculation is carried out by incorporating sequential modular approach. Then a model of the Bayer process digester is programmed and several simulations are carried out using this model. Results of the mass balance calculation revealed that changes in the extent of the digestion reaction, which is a function of temperature and caustic concentration, and washing efficiency may have a 2.07% decrease on the amount of red mud produced,which implies nearly 10,000 tons of decline per annum, while amount of hydrate produced is increased by 4.52%. A 7.40 % decrease on the amount of red mud produced on dry basis per kg of hydrate was found to be achievable. Optimum operating temperature for the digester was calculated as 277.3 &deg / C.

Στην παρούσα διατριβή εξετάστηκε η δυνατότητα χρήσης της σιδηραλούμινας, του προϊόντος που προέρχεται από την επεξεργασία της ερυθράς ιλύος, ως πρώτη ύλη και ως πρόσθετο στη διεργασία παραγωγής τσιμέντου. Η ερυθρά ιλύς αποτελεί το παραπροϊόν της επεξεργασίας του βωξίτη για την παραγωγή αλούμινας μέσω της διεργασίας Bayer. Αποτελείται από το τμήμα του βωξίτη που δεν αντιδρά, το τμήμα του βωξίτη που έχει αντιδράσει προς το σχηματισμό άλλων ενώσεων, από συστατικά που εισάγονται στη διεργασία και από τα υδροξείδια του αργιλίου που δεν ανακτώνται. Η απομάκρυνση του νερού από την ερυθρά ιλύ έχει ως αποτέλεσμα την παραγωγή ενός στερεού υπολείμματος, της σιδηραλούμινας. Αν και υπάρχουν αρκετές διαθέσιμες τεχνολογίες για απομάκρυνση του νερού, η χρήση πρέσας φίλτρων υψηλής πίεσης συγκεντρώνει πολλά προτερήματα. Η μελέτη απομάκρυνσης του νερού πραγματοποιήθηκε σε μια εργαστηριακής κλίμακας πρέσα φίλτρων, όπου και διαπιστώθηκε ότι είναι δυνατή η παραγωγή στερεού υπολείμματος (κέικ) με περιεκτικότητα ~35% σε νερό. Η έρευνα επεκτάθηκε σε πιλοτικής κλίμακας πρέσα φίλτρων όπου εξετάστηκαν περισσότερες παράμετροι, όπως ο τύπος του φίλτρου και το υλικό από το οποίο είναι φτιαγμένο. Τα αποτελέσματα έδειξαν ότι είναι δυνατή η παραγωγή στερεού υπολείμματος με σταθερό ποσοστό υγρασίας μεταξύ 27% και 32% και πυκνότητα περίπου 2g/cm3, οδηγώντας στην εγκατάσταση μιας βιομηχανικής πρέσας φίλτρων υψηλής πίεσης, η οποία λειτουργεί από την αρχή του 2006 με επιτυχία στο «Αλουμίνιο της Ελλάδας». Η χημική ανάλυση της σιδηραλούμινας καταδεικνύει ότι πρόκειται για ένα υλικό που μπορεί να χρησιμοποιηθεί σαν δευτερεύουσα πρώτη ύλη στην βιομηχανία τσιμέντου ως φορέας σιδήρου. Η μελέτη της καταλληλότητάς της πραγματοποιήθηκε με το σχεδιασμό μιγμάτων πρώτων υλών για την παραγωγή τσιμέντου τύπου Portland στα οποία η σιδηραλούμινα συμμετείχε σε ποσοστά έως 5%κ.β. Τα αποτελέσματα έδειξαν ότι τα παραγόμενα με σιδηραλούμινα τσιμέντα παρουσιάζουν ίδια ποιοτικά ορυκτολογική σύσταση με το αντίστοιχο αναφοράς ενώ οι φυσικές τους ιδιότητες όπως η απαίτηση σε νερό και ο χρόνος πήξης βρίσκονται στα ίδια επίπεδα. Όσον αφορά στις μηχανικές τους ιδιότητες, οι τιμές που ελήφθησαν κατατάσσουν όλα τα τσιμέντα στην κατηγορία των 42.5N. Ειδικότερα τα τσιμέντα με σιδηραλούμινα κατατάσσονται σε υψηλότερη κατηγορία (52.5N) λόγω των αυξημένων πρώιμων αντοχών (2 ημερών). Τέλος, τα παραγόμενα με σιδηραλούμινα τσιμέντα έδειξαν ότι απελευθερώνουν μεγαλύτερη ποσότητα υδατοδιαλυτού χρωμίου από το τσιμέντο αναφοράς, απόρροια του υψηλότερου αρχικού φορτίου ολικού χρωμίου που περιέχουν. Οι βιομηχανικές δοκιμές που ακολούθησαν στις βιομηχανίες ΤΙΤΑΝ και ΑΓΕΤ ΗΡΑΚΛΗΣ έδειξαν ότι η προσθήκη σιδηραλούμινας σε επίπεδα 2.7%κ.β οδηγεί σε βελτίωση της εψησιμότητας του μίγματος λόγω της μείωσης του πυριτικού δείκτη. Επίσης η προσθήκη σιδηραλούμινας προς αντικατάσταση του χρησιμοποιούμενου πυρίτη στο μίγμα οδήγησε στη μείωση των ιχνοστοιχείων Mn, Pb, Zn και Cu στο μίγμα ενώ αύξησε το ποσοστό του Cr. Τα αποτελέσματα για το παραγόμενο κλίνκερ έδειξαν ότι η προσθήκη δεν επηρέασε ποιοτικά τις σχηματιζόμενες ορυκτολογικές φάσεις ενώ οι αντοχές που παρουσίασαν τα παραγόμενα τσιμέντα φτάνουν τα 27.7MPa για τις πρώτες 2 ημέρες και τα 51.6MPa μετά από 28 ημέρες. Η επίδραση της προσθήκης στους αέριους ρύπους των εργοστασίων ήταν μηδενική, καθώς οι τιμές αυτών παρέμειναν στα ίδια επίπεδα κατά τη διεργασία παραγωγής. Προκειμένου να αξιολογηθεί η περιβαλλοντική συμπεριφορά των παραγόμενων με σιδηραλούμινα τσιμέντων, πραγματοποιήθηκαν δοκιμές εκπλυσιμότητας. Για τις δοκιμές χρησιμοποιήθηκαν δύο δείγματα τσιμέντου, ένα χωρίς σιδηραλούμινα (αναφορά) και ένα 2%κ.β σιδηραλούμινα. Οι ανωτέρω δοκιμές πραγματοποιήθηκαν υπό το πρίσμα δύο προτύπων, του NEN 7345-tank test που αναφέρεται σε μονολιθικά υλικά (service life scenario) και του prEN 14429-pH dependence test που αναφέρεται σε κοκκώδη υλικά (“second life” scenario). Σύμφωνα με τη χημική ανάλυση των δύο τσιμέντων, το τσιμέντο με σιδηραλούμινα παρουσιάζει μεγαλύτερο αρχικό φορτίο σε Cr, Ni και V από το αντίστοιχο αναφοράς. Το παραπάνω γεγονός δεν επηρεάζει την απελευθέρωση στην περίπτωση του μονολιθικού υλικού, όπου τόσο για την περίπτωση του Cr όσο και για αυτές των Ni και V παρατηρούνται ίδια επίπεδα απελευθέρωσης τόσο για το δοκίμιο αναφοράς όσο και για το δοκίμιο με σιδηραλούμινα. Στην περίπτωση του κοκκώδους (θραυσμένου) υλικού η απελευθέρωση των ιχνοστοιχείων στο περιβάλλον είναι ανάλογη του αρχικού τους φορτίου και εντείνεται καθώς η ισορροπία μετατοπίζεται προς χαμηλότερα pH. Οι σύγχρονες τάσεις που αφορούν την εξοικονόμηση ενέργειας και την προστασία του περιβάλλοντος έστρεψαν την έρευνα στη δυνατότητα προσθήκης σιδηραλούμινας ως πρώτη ύλη για την παραγωγή τσιμέντων μπελιτικού τύπου. Η διαφορά των ανωτέρω τσιμέντων με τα τσιμέντα τύπου Portland είναι τα μειωμένα επίπεδα της φάσης του πυριτικού τριασβεστίου (C3S) απόρροια της χαμηλότερης θερμοκρασίας έψησης (~1350οC) γεγονός που τα κατατάσσει στην κατηγορία των φιλικών προς το περιβάλλον τσιμέντων. Τα αποτελέσματα έδειξαν ότι η χρήση σιδηραλούμινας για την παραγωγή μπελιτικών τσιμέντων είναι εφικτή αλλά και ότι τα τσιμέντα αυτού του τύπου έχουν ένα σαφές μειονέκτημα έναντι των Portland, τις χαμηλές πρώιμες αντοχές τους. Το μειονέκτημα αυτό αντιμετωπίστηκε με την εισαγωγή γύψου στο μίγμα των πρώτων υλών που είχε ως επακόλουθο τη δημιουργία της υδραυλικής ένωσης 4CaO.3Al2O3.SO3 κατά τη διαδικασία έψησης. Τέλος εξετάστηκε η δυνατότητα της σιδηραλούμινας να δράσει ως υπόστρωμα για την ρόφηση του εξασθενούς χρωμίου (Cr(VI)) σε υδατικά διαλύματα προκειμένου να χρησιμοποιηθεί ως πρόσθετο στο τελευταίο στάδιο της παραγωγής τσιμέντου. Η μελέτη πραγματοποιήθηκε λαμβάνοντας υπ’ όψιν παραμέτρους όπως το pH του διαλύματος, ο χρόνος επαφής και η αναλογία υγρού προς στερεό (l:s ratio). Τα αποτελέσματα κατέδειξαν ότι η σιδηραλούμινα εμφανίζει ροφητικές ιδιότητες οι οποίες αυξάνονται εάν προηγηθεί ένα στάδιο χημικής και θερμικής επεξεργασίας αυτής. Αυτό οφείλεται στην αύξηση της ειδικής επιφάνειας της σιδηραλούμινας από τα 10m2 g-1 στα 70m2 g-1 λόγω της αύξησης του μικροπορώδους της. Τα επίπεδα ρόφησης χρωμίου για την επεξεργασμένη σιδηραλούμινα έφτασαν σε ιδανικές συνθήκες στα 0.82mg g-1. Ο μηχανισμός της ρόφησης περιγράφεται από την ισόθερμη Langmuir ενώ περιορίζεται σε μια στενή περιοχή τιμών του pH ανάμεσα στο 5 και στο 6. / In the present thesis the potential utilization of ferroalumina, a by-product that derives from the dewatering of red mud, as a raw material as well as an additive material in the cement production route is examined. Red mud is the main by-product that derives from the digestion of bauxite ores during Bayer process in order to produce alumina. It comprises from the ore part that has not reacted, the part that has reacted and has formed other than the desired compounds, from supplementary materials that were introduced during the procedure and from aluminium hydroxides that were not recovered. The removal of red mud’s water content leads to the production of ferroalumina. Although there are many ways of removing the water, the use of a filter press has many advantages. The laboratory study of the water removal from red mud by means of a filter press led to the formation of a cake with ~35%wt of water. Parameters, such as the filter type and the material that it comprises were examined with the further use of a pilot scale filter press. The results indicated that the filter press can produce a cake with constant water amount between 27% and 32%wt and density 2g/cm3. The latter results, led to the installation of an industrial high pressure filter press, which is in operation since the beginning of 2006, in the Aluminium Hellas industry. Ferroalumina’s chemical analysis indicates that it can be used as a secondary material in the cement industry, mainly as an iron oxide carrier. The study for its suitability was performed by preparing Portland cement raw mixtures introducing ferroalumina up to 5%wt are a raw material. Consequently, the raw mixtures were fired up to 1550oC in order to produce clinker and co-grounded with gypsum in order to produce Portland cement. The results indicate that the produced ferroalumina cements presents similar mineralogical composition with the cements without ferroalumina whilst their physical properties such as the water demand and the setting time are at the same levels. Regarding their mechanical properties, the obtained compressive strength values are ranking all the cements in the 42.5N category. Especially the ferroalumina cements are falling into a higher category and more specifically in the 52.5N category due to their high early day strengths. Finally, the study indicate that the ferroalumina cements presents higher amounts of water soluble chromium than the cement without ferroalumina (reference), most probably due to their higher initial amount of total chromium. The industrial trials that were performed by the Greek cement industries TITAN and AGET Heracles showed that the addition of ferroalumina up to 2.7%wt improves the burnability of the mixture due to the silica modulus reduction. The substitution of the raw material pyrite from the ferroalumina, led to the reduction of Mn, Pb, Zn and Cu on the raw mixture whilst it increased the Cr percentage. The results for the produced clinker indicate that the ferroalumina addition did not affect the formatted mineralogical phases. The compressive strength values of the obtained cements, was 27.7MPa after the first 2 days and 51.6MPa after 28 days of curing. The flue gas emissions were at the same levels during the cement production indicating that the ferroalumina addition does not affect that part of production either. In order to evaluate the environmental behaviour of the ferroalumina cements, two types of leaching tests, which refer to different field scenarios, were employed. The NEN 7345-tank test which refers to monolithic materials (“service life” scenario) and the prEN 14429-pH dependence test, which concerns granular materials (“second life” scenario). Two different cement samples were used for the above mentioned tests. The first one was produced without ferroalumina (reference sample) whilst the second one was produced with a 2%wt ferroalumina addition. The chemical analysis of the cement with ferroalumina showed that it presents greater content of Cr, Ni and V than the reference cement. The latter does not affect leaching in the service life scenario. More specifically in the case of Cr the reference cement presents the same leaching amount with the ferroalumina cement whilst in the case of Ni and V no leaching is observed for any of the two cement samples. During the “second life” scenario the leaching is greater in the case of the ferroalumina cement. The latter is related to the greater initial content of the above mentioned cement in Cr, Ni and V. The leaching behaviour is for both cements pH sensitive as higher leaching values for Cr and Ni are observed while the pH shifts to lower values. The new trends concerning the sustainable development through energy conversion and environmental protection have led the current study in the utilization of ferroalumina in the field of belite cements. The main difference of the above mentioned cements from the Portland cements is the low content in calcium silicate (C3S) mainly due to the lower firing temperature (~1350οC). The latter ranks the above mentioned cements in the environmental friendly cements category (green cements). The obtained results indicate that the use of ferroalumina as a raw material for the production of belite cements is possible as well as that the produced cements have a certain drawback when compared with the OPC. The lack of C3S leads to low early day strength. This drawback was confronted with the introduction of gypsum in the raw mixture which led to the formation of the hydraulic compound 4CaO.3Al2O3.SO3 (Klein’s compound) during the firing procedure. The last chapter deals with the possibility of utilize ferroalumina as a substrate for the absorption of hexavalent chromium in order to use it as an additive material in the last stage of cement production. The study examined parameters such as the pH of the solution, the contact time and the liquid to solid ratio (l:s ratio). The results indicate that the ferroalumina is able to absorb chromium and that this ability increases if a stage of chemical and thermal treatment is employed before. The treatment enhances ferroalumina’s absorption ability due to an increase of specific surface from 10m2 g-1 to 70m2 g-1. The absorbance mechanism is described with the Langmuir model and the best results are obtained for pH 5 and contact time 1h. The amount of chromium that is absorbed from each grammar of ferroalumina in the above mentioned conditions is 0.82mg.

The estimated global production of red mud, a by-product of alumina production, is ~120 million t per year. Little is known about the long-term chemical, physical and ecological responses in aquatic ecosystems following pollution with red mud. To date, no whole-lake assessment of the impact of red mud and recovery trajectories has been conducted. Kinghorn Loch, Fife, Scotland, is an important example of a red mud polluted aquatic ecosystem. This is due mainly to the availability of long-term data documenting changes in the lake during the pollution and recovery following diversion of red mud leachate in 1983 to date. Long-term data were assessed to determine the time scale of recovery for a range of specific pollutants in the surface waters of Kinghorn Loch, and field surveys and a laboratory controlled experiment were conducted to investigate lake sediment-pollutant interactions and arsenic (As) species bioaccumulation in aquatic plants. Results showed recovery of the lake water column, with a significant decrease of pH and the concentrations of all red mud constituents in surface water since the cessation of pollution. Using generalised additive models the chemical recovery period was 5 years for pH and from 22 to 26 years for As, vanadium (V) and phosphorus (P), with aluminium (Al) still not reaching the end-point recovery following this period. A 12- month field survey showed that concentrations of phosphate (PO4-P), total phosphorus (TP), dissolved and total As and V in lake water varied significantly throughout the year, with depth of overlying water contributing to variation in P concentrations in water above sediment. A range of physico-chemical factors, including dissolved oxygen (DO), pH and concentrations of pollutant binding element controlled seasonal and spatial variations in water column contaminant concentrations. The behaviour of V differed from As and P concentrations in water, with maximum V concentrations occurring in spring and the highest concentrations of As and P in surface water and dissolved As and PO4-P in water above sediment observed in summer. With the exception of V in deeper layers of the water column in spring and winter, observed total As and V concentrations met standards for Protection of Aquatic Life in the UK (50 and 20 μg L-1, respectively). Sediment in Kinghorn Loch is still contaminated 30 years into the lake recovery period. The highest seasonal mean concentrations in the upper (0-4 cm) sediment layer were 231 mg kg-1 for V and 185 mg kg-1 for As, the latter considerably exceeding Canadian Sediment Quality Guidelines for the Protection of Aquatic Life for As (17 mg kg-1). Evidence from the laboratory experiment and the field observations suggests that the lake still processes red mud contaminants, with seasonal mobilisation of As and P from lake sediment under reducing conditions. In contrast, release of V from sediment into overlying water appeared not to be driven predominantly by redox conditions, but instead by interactions between pH, competitive ion concentrations and DO. Higher pollutant concentrations observed throughout the year in deeper layers of the water column compared to surface water indicated that the impact of sediment on the water column is generally confined to the bottom waters of the lake. Macrophytes in Kinghorn Loch contained relatively high concentrations of As, predominantly in the inorganic form which is most toxic to organisms. The highest As content measured in roots of Persicaria amphibia (L.) Gray (40.4 – 218 mg kg-1) greatly exceeded the 3 – 10 mg kg-1 range suggested as a potential phytotoxic level. Accumulation of toxic As species by plants suggested toxicological risk to higher organisms in the food web and indicated that ecological recovery of the lake is still in progress. The results of this research at Kinghorn Loch will help water resource managers to understand not only the environmental and human health effects of multiple pressures related to red mud pollution, but also the likely recovery time scales in relation to water quality targets.

Submitted by Mayara Sakamoto Lopes (mayarasakamoto@hotmail.com) on 2017-10-26T16:08:16Z No. of bitstreams: 1 Dissertação_Mayara Sakamoto Lopes.pdf: 6344472 bytes, checksum: 53e6e860cec7380199632c6eda1ee064 (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-10-31T17:53:45Z (GMT) No. of bitstreams: 1 lopes_ms_me_bauru.pdf: 6344472 bytes, checksum: 53e6e860cec7380199632c6eda1ee064 (MD5) / Made available in DSpace on 2017-10-31T17:53:45Z (GMT). No. of bitstreams: 1 lopes_ms_me_bauru.pdf: 6344472 bytes, checksum: 53e6e860cec7380199632c6eda1ee064 (MD5) Previous issue date: 2017-10-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As indústrias têxteis caracterizam-se pelos elevados volumes de água consumida e de efluente lançado, o qual, por possuir coloração intensa, reduz a penetração da luz solar nos corpos hídricos receptores e afeta a fotossíntese. Nesse trabalho, avaliou-se a adsorção do corante Azul Reativo 19 (RA19) por carvão ativado comercial (CAP), CAP tratado por ozônio (CAP – O3), lama vermelha (LV) e LV tratada por ozônio (LV – O3). Os adsorventes foram caracterizados quanto ao pH, condutividade elétrica, número de iodo, índice de azul de metileno, granulometria, composição química, mineralogia e micromorfologia. Investigou-se a influência do pH e da temperatura no processo de adsorção. Além disso, analisou-se a cinética da adsorção de RA19 a diferentes concentrações iniciais (300, 500, 1000, 2000 e 3000 mg/L), por meio dos modelos de pseudo primeira ordem, pseudo segunda ordem, difusão intrapartículas e Elovich; e avaliou-se a capacidade de adsorção dos quatro adsorventes, por isotermas de Langmuir e Freundlich. Os resultados indicaram que o tratamento por ozônio não altera significativamente a composição química do CAP e da LV, mas possivelmente reduz o volume de mesoporos do CAP. A eficiência de remoção do RA19 por CAP independe do pH inicial da solução, mas por LV, é favorecida em pH mais baixo (igual a 3). Observou-se que 120 minutos são suficientes para atingir o equilíbrio da reação; e que o aumento da concentração inicial de corante reduz a eficiência de remoção, mas aumenta a capacidade de adsorção. Os dados experimentais ajustaram-se aos modelos de pseudo segunda ordem e de Elovich, indicando que o processo é controlado por quimissorção. Para todos os adsorventes, a adsorção do RA19 é multicamada em superfícies heterogêneas, visto que os dados se ajustaram à isoterma de Freundlich. Os resultados termodinâmicos sugeriram que existe afinidade entre o RA19 e os adsorventes, sendo que a reação ocorre espontaneamente; além disso, a adsorção por CAP e por CAP – O3 é endotérmica, e a adsorção por LV e por LV – O3 é exotérmica. A maior (216,4 mg/g) e a menor (138,7 mg/g) capacidade de adsorção foram obtidas pelo CAP e pelo CAP – O3, respectivamente. Concluiu-se que a ação do ozônio desfavoreceu a adsorção do RA19, em termos de fração residual, quantidade de corante adsorvido, velocidade de reação, e capacidade máxima de adsorção. / Textile industries are characterized by high water consumption and by large effluent release, which is strongly colored and therefore reduces sunlight penetration into water and affects photosynthesis. This study evaluated the adsorption of Reactive Blue 19 (RB19) by commercial activated carbon (PAC), PAC treated by ozone (PAC – O3), red mud (RM) and RM treated by ozone (RM – O3). The adsorbents were characterized by pH, electric conductivity, iodine number, Methylene Blue index, granulometry, chemical and mineralogical composition and micromorphology. Influence of pH and temperature was investigated. Additionally, the RB19 adsorption kinetics was evaluated at different initial concentrations (300, 500, 1000, 2000 and 3000 mg/L) with the pseudo first order, pseudo second order, intraparticle diffusion and Elovich models; and the adsorptive capacity of the adsorbents was investigated by Langmuir and Freundlich isotherms. The results showed that ozone treatment does not significantly change the chemical composition of PAC and RM, but it possibly reduces PAC’s mesopore volume. The initial pH does not influence the efficiency of RB19 removal by PAC, but it influences the removal by RM, being higher at lower pH (equal to 3). The adsorption reached an equilibrium state at about 120 minutes from the beginning of the experiments; and it was observed that increasing initial dye concentration, removal efficiency was reduced, while adsorption capacity was improved. The experimental data fitted well to the pseudo second order and Elovich kinetics models, which indicate that the process is controlled by chemisorption. The RB19 removal obeys the Freundlich isotherm model, showing multilayer adsorption on heterogeneous surface. The thermodynamic studies indicated that RB19 has affinity to the adsorbents, and the reaction occurs spontaneously; furthermore, the adsorption by PAC and PAC – O3 is endothermic, while the adsorption by RM and RM – O3 is exothermic. The highest (216.4 mg/g) and the lowest (138.7 mg/g) adsorption capacity were obtained by PAC and PAC – O3, respectively. It was concluded that ozone negatively affects RB19 adsorption, in terms of residual fraction, amount of dye adsorbed, reaction rate and maximum adsorption capacity.

A questão ambiental é um tema muito importante em nossos dias, é por isso que muitas empresas têm interesse em valorizar seus resíduos, seja para minimizar custos ou para vender um produto que pode ser usado como matéria-prima em outras indústrias. O estabelecimento de uma legislação mais rigorosa sobre o destino final dos resíduos sólidos tem sido acompanhado, de uma progressiva rejeição das disposições tradicionalmente aceitas. Por isso é necessário estudar novas alternativas para a disposição de resíduos industriais e pesquisar algumas aplicações para transformá-los em materiais com um valor agregado. Este trabalho tem como objetivo estudar a incorporação de dois resíduos em massas cerâmicas: lodo gerado no processo de tratamento de esgoto doméstico e lama vermelha (resíduo do processo Bayer de produção de alumina). Além desses resíduos foram empregadas umas argilas que são usadas na fabricação de materiais de cerâmica vermelha. Tanto os resíduos como as argilas tiveram sua composição mineralógica caracterizada por difração de raios X (DRX) e composição química por fluorescência de raios X (FRX). Esses resíduos foram misturados com argila e foram produzidas massas cerâmicas para avaliar seu desempenho nas propriedades fundamentais (resistência mecânica à flexão, densidade aparente, porosidade e absorção de água). Os corpos de prova foram conformados por prensagem uniaxial (25 MPa, 60×20×~4 mm³), e foram estudadas várias composições e duas temperaturas de queima (950°C e 1050°C), temperaturas usuais de queima em produtos de Cerâmica Vermelha. Alguns dos resultados obtidos cumprem com os parâmetros exigidos para a fabricação de diferentes tipos de produtos cerâmicos como tijolos, telhas e revestimentos cerâmicos. / Nowadays the environmental protection is an important matter. For that reason many companies are concerned about giving value to their residues, either to minimize operation costs or to sell raw material to other industries. With more restrictive legislation about wastes management, the traditional disposals are being rejected. Therefore, it is necessary to study new alternatives of final disposal and research new applications to transform industrial wastes into added-value products. This work aims to study the incorporation of two industrial wastes in ceramic materials; sewage sludge from a municipal wastewater treatment plant and red mud (a by-product of the Bayer process to produce alumina). In addition to those residues, it was used two local clays that are usually incorporated in ceramic bricks. Both residues as well as the clay were characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF). The residues and the clay were mixed, and prismatic probes were conformed to evaluate their technological properties (bending resistance, bulk density, porosity and water absorption). The ceramic probes were pressed uniaxially (25 MPa, 60×20×~4 mm³) and two temperatures (950°C and 1050°C), normally used in traditional ceramic industry, were studied. Some of the results fulfill the required parameters for the fabrication of different kinds of ceramic products as bricks, roof tiles and floor tiles.

A lama vermelha é o resíduo gerado pela Indústria do Alumínio. Assim como outros resíduos industriais apresenta características complexas com inúmeras dificuldades de manipulação, além de ser um material perigoso pela sua baixa granulometria e alcalinidade. É um resíduo com potencial poluidor alto, agravado pela forma de disposição vulnerável geralmente adotada, sendo esta a disposição do resíduo em lagoas projetadas para esta finalidade. O estudo e desenvolvimento de alternativas sustentáveis para a utilização da lama vermelha devidamente tratada como matérias-primas de outros processos são tendências importantes e necessárias no contexto mundial de preservação do meio ambiente. O objetivo deste estudo é compreender o comportamento da lama vermelha sob a influência de diferentes temperaturas de tratamento térmico. Baseados nos efeitos de redução de área e transformações de fases, característicos dos processos térmicos, adotou-se um foco de análise voltado para a redução pH e dos íons livres. A identificação dos pHs adequados de análise da concentração de íons solúveis foi feita com base nas curvas de mobilidade eletroforética e condutividade. Os resultados obtidos para as amostras calcinadas mostraram queda do pH inicial das dispersões e da concentração dos íons solubilizados. Esse efeito pode ser atribuído a redução de área e a incorporação de íons à estrutura, o que assegura ao resíduo menor reatividade. / Red mud is the waste generated by Aluminium Industry, like other industrial wastes, has complex features with several difficulties in handling, as well as being a hazardous material because of its low particle size, alkalinity and high amount generated. It is a waste with high pollution potential, compounded by the vulnerability of the disposition generally adopted, usually in lagoons designed for this purpose. The study and development of sustainable alternatives for the use of properly treated red mud, as raw material of other processes, are important tendencies and necessaries in the global context of environmental preservation. However, this work deals the thermal treatment as method to modify the characteristics of the waste, suggesting the reduction of alkalinity with the lower leaching of alkaline ions. This approach can be a discarding alternative most reliable and safe for the environment. The objective of this study is understand the red muds behavior using thermal treatment. Based on the reduction effects of the area and phase transformations characteristic of thermal process, the analysis was taken observing the reduction of free ions and pH. Identification of correct pH of analyse of soluble ions concentration was based at mobility electrophoretic and conductivity graphics. The results of calcined samples showed reduction of initial pH and the concentration of soluble ions. This effect could be assigned to the area reduction and ions incorporation at structure, which ensures the residue lower reactivity.

Neste trabalho, vidros contendo um resíduo industrial denominado lama vermelha, foram desenvolvidos e caracterizados. Foi utilizada a quantidade mínima de 60% em massa de lama vermelha na produção dos vidros para promover a utilização desse resíduo. De acordo com os resultados de difração de raios X obtidos, observa-se que é possível produzir materiais a partir da lama vermelha com fases amorfas consideráveis, embora fases cristalinas referentes ao Fe originário do resíduo estejam presentes. O material denominado 60L40S, o qual possui 60% em massa de lama vermelha na sua composição nominal, apresentou as melhores propriedades dentre as composições estudadas, porém apresentou também alta temperatura de fusão. Ajustes na composição desse material foram realizados buscando diminuir essa temperatura. Os resultados mostram que os ajustes foram satisfatórios no desempenho de diminuir a temperatura de fusão, porém perdas na propriedade química desse material foram observadas. Elementos comumente encontrados na composição química de rejeitos nucleares foram adicionados aos vidros produzidos neste trabalho visando estudar os efeitos dessa adição nas propriedades químicas e térmicas desses materiais. Foi observado que é possível adicionar até 15% em massa de elementos simuladores aos materiais produzidos e essa adição promove a diminuição da temperatura de fusão. Acima de 15% em massa os elementos adicionados se precipitam na estrutura do material. Foi observado que, embora haja perdas na durabilidade química do material 60L40S após a adição dos elementos simuladores, esse material, quando em contato com água, mantém os elementos simuladores confinados em sua estrutura. Esse resultado é promissor, pois sugere que o material 60L40S é capaz de imobilizar em sua estrutura elementos provenientes de rejeitos nucleares. / Glasses based on red mud, a residual material from bauxite processing, were developed and characterized in this work. In order to promote its use, a minimum 60 wt% of red mud was used in the production of the glasses. According to XRD results, materials containing considerable amorphous phases were produced when using red mud as raw material. These amorphous phases were observed even though crystalline phases associated to Fe coming from the red mud itself were present. The material denominated 60L40S, which has a nominal composition of 60 wt% red mud showed the best properties comparing with the others compositions studied. However, these materials presented a high melting temperature. Changes in the composition of this material were made with the objective of lowering this temperature. Results indicated that the changes made to the material were successful in the reduction of the melting temperature. However, a reduction in the chemical properties of the resulting material was observed. Elements usually found in the chemical composition of nuclear wastes were added to the glasses produced. It was done with the objective of determining the effect of these elements on the chemical and physical properties of the red mud based glasses obtained. It was found that it was possible to add up to 15 wt% of these elements to the materials produced. The addition of these simulants materials promoted a reduction in the melting temperature of the resulting material. Above 15 wt%, the added elements precipitate in the structure of the resulting material. Even though the reduction in the chemical durability of the 60L40S material when simulant elements were added, it was observed that this material contained the simulant elements confined in its structure when in contact with water. This is a promising result, since it indicates that the 60L40S has the potential to immobilize elements from nuclear wastes.

Catalytic hydrodeoxygenation (HDO), is an effective process to convert oxygenated compounds to hydrocarbons. This process is widely used for improving the negative properties of biomass-derived pyrolysis oils (bio-oils) such as high acidity, poor stability, and low heating value. During this process oxygen is removed from the bio-oil in the form of water, thus the liquid product of HDO process consists of aqueous phase and hydrocarbon phase that can be easily separated. Synthesis of efficient HDO catalyst has been a major challenge in the field of bio-oil upgrading. Red mud, which is an alkaline waste from alumina industry was used to develop a new red mud-supported nickel catalyst (Ni/RM) for the HDO of pinyon-juniper catalytic pyrolysis oil. The new catalyst was more effective than the commercial Ni/silica-alumina catalyst for the HDO of organic phase pyrolysis oil, the aqueous phase pyrolysis oil, and bio-oil model compounds. Less hydrogen was consumed in the case of Ni/RM and more liquid hydrocarbon yield was obtained compared to the commercial catalyst. In addition to HDO reactions, the Ni/RM catalyst catalyzed ketonization and carbonyl alkylation reactions that was important to produce liquid hydrocarbon from low molecular weight oxygenated compounds. Unlike the commercial catalyst, Ni/RM was regenerable by burning off the deposited coke and activation by reduction using hydrogen.