Ο Φώσφορος είναι από τα κυριότερα θρεπτικά συστατικά που συμβάλλουν στην ανάπτυξη των φυτών και άλλων βιολογικών οργανισμών. Η παρουσία του ωστόσο σε αυξημένα επίπεδα συγκεντρώσεων στα επιφανειακά ύδατα απορροής, συμβάλλει στην δημιουργία ανεπιθύμητου ευτροφισμού. Η επεξεργασία των αστικών υγρών αποβλήτων, πριν την τελική διάθεση τους στους υδάτινους αποδέκτες, για την απομάκρυνση του διαλελυμένου φωσφόρου, είναι απαραίτητη. Ουσιαστική ωστόσο συμβολή στην αειφόρο ανάπτυξη συνιστά η ανάκτηση του φωσφόρου με την μορφή προϊόντων τα οποία μπορούν να χρησιμοποιηθούν ως λιπάσματα. Αυτό αποτέλεσε και τον βασικό στόχο της παρούσας εργασίας. Συγκεκριμένα, στην παρούσα εργασία μελετήθηκε η δυνατότητα ανάκτησης των ανόργανων φωσφορικών από προσομοιωμένο αστικό υδατικό απόβλητο, με την κρυστάλλωση MgNH4PO4∙6H2O (Στρουβίτη). Διερευνήθηκε η δυνατότητα ανάκτησης του φωσφόρου με την μορφή στρουβίτη σε ρευστοποιημένη κλίνη με πληρωτικό υλικό πυριτικά στερεά. Η κρυστάλλωση έγινε σε υπέρκορα αλλά σταθερά διαλύματα και μελετήθηκε η μόνιμη κατάσταση η οποία μπορεί να αναπτυχθεί με συνεχή τροφοδοσία ανακύκλωσης του διαλύματος. Έγινε παραμετρική μελέτη των συνθηκών λειτουργίας της κλίνης με στόχο την μεγιστοποίηση της ανάκτησης φωσφόρου σε pH═6.5 και θ═25C. Το στερεό που καταβύθισθηκε από τα υδατικά διαλύματα, χαρακτηρίσθηκε με περίθλαση ακτίνων -Χ(XRD) και ηλεκτρονική μικροσκοπία σάρωσης (SEM). Διερευνήθηκε ο μηχανισμός της ετερογενούς πυρηνογενέσεως και αναπτύξεως κρυστάλλων στρουβίτη στην επιφάνεια του πληρωτικού υλικού της ρευστοποιημένης κλίνης με μετρήσεις του ρυθμού κρυστάλλωσης συναρτήσει του υπερκορεσμού. Οι μετρήσεις αυτές έδειξαν ότι το καθορίζον την ταχύτητα στάδιο ήταν η διάχυση των δομικών μονάδων στην επιφάνεια των κρυσταλλιτών του πληρωτικού υλικού, το οποίο ήταν καιτο υπόστρωμα για την κρυσταλλική ανάπτυξη. Η κρυσταλλική ανάπτυξη του στρουβίτη, έγινε επιλεκτικά στους κρυσταλλίτες του πληρωτικού υλικού. / Phosphorus is one of the most essential nutrients for the growth of plants and other organisms. However, the presence at high concentrations in surface waters, contributes to the development of eutrophication.The treatment of municipal wastewaters, before final disposal in aquatic systems, is necessary for the removal of dissolved phosphorus. Alternatively, phosphorus recovery in the form of solids which may be used as fertilizers is a significant contribution to the sustainable development.In the present work, it was attempted to recover P from simulated municipal wastewater in the form of struvite (MgNH4PO4∙6H2O) by crystallization in a fluidized bed reactor(FBR).Silicates (quartz and silica gel) were used as substrates in the FBR.The FBR was fed with kinetically stable solutions, supersaturated with respect to struvite. The solutions were introduced in the silicate bed by a peristaltic pump and were recirculated through a reservoir. Measurements of the solution pH and of the concentrations of Mg and P were used to monitor the process and for the measurement of induction times and rates of precipitation. A parametric study of the operating conditions, in the FBR was carried out in order to investigate the possibilities of P recovery at pH 6.50 and θ═25C. The mechanism of heterogeneous nucleation and crystal growth of struvite crystals on the surface of the filling particles(quartz)of the FBR, was investigated from measurements of the crystallization rate as a function of the solution supersaturation.In all cases the crystalline material forming out of the supersatured solutions was struvite and was identified by X-Ray Diffraction (XRD)and Scanning Electron Microscopy (SEM). The kinetics results suggested that the rate determining step was the diffusion of the structural units on the surface of the substrate particles. The induction times preceding the onset of the selective crystallization of struvite on the quartz particls in the FBR were inversely proportional with the solution supersaturation.From this dependence a value of ca. 22mJm^-2 was calculated for the surface energy of the overgrowth. Induction times were shorter and crystal growth rates were faster the higher the fluid velocity in the FBR, in agreement with literature reports.

O Φώσφορος είναι βασικό συστατικό των αστικών αποβλήτων, ο οποίος συγκεντρώνεται στους υδάτινους αποδέκτες προκαλώντας κυρίως προβλήματα ευτροφισμού. Τα παγκόσμια αποθέματα ορυκτού φωσφόρου μειώνονται λόγω της αυξημένης ζήτησης, έτσι κρίνεται απαραίτητο η κατά κάποιον τρόπο ανακύκλωση του. Μια από τις εναλλακτικές και πολλά υποσχόμενες μεθόδους για την ανάκτηση του φωσφόρου από την επεξεργασία των υγρών αποβλήτων είναι η δέσμευση του φωσφόρου, μέσω της κρυστάλλωσης, υπό την μορφή φωσφορικών αλάτων όπως ο στρουβίτης (ΜgNH4PO4.6H2O). O στρουβίτης χρησιμοποιείται απευθείας ως βραδέως αποδεσμευόμενο λίπασμα, το οποίο λόγω της χαμηλής του διαλυτότητας, εξασφαλίζει, την ελεγχόμενη παροχή θρεπτικών συστατικών φωσφόρου και αζώτου, απαραίτητων για την ανάπτυξη των φυτών. Στη παρούσα εργασία, δοκιμάστηκαν δύο τύποι αντιδραστήρων, ένας αντιδραστήρας ρευστοποιημένης κλίνης (FBR) και ένας αντιδραστήρας διαλείποντος έργου (Batch) με συνθετικό απόβλητο σε pH 6.50 στους 25οC. Η στοιχειομετρική αναλογία 1:1:1 των πλεγματικών ιόντων του στρουβίτη, Mg:N:P, διατηρήθηκε σε όλα τα πειράματα. Η καταβύθιση στρουβίτη σε υπέρκορα διαλύματα εξαρτάται κυρίως από τον υπερκορεσμό της καταβυθιζόμενης φάσης, τη θερμοκρασία και τη παρουσία ξένων ιόντων ή επιμολύνσεων. Πραγματοποιήθηκαν πειράματα αυθόρμητης καταβύθισης του στρουβίτη σε συνθήκες σταθερού pH για τον καθορισμό του εύρους της μετασταθούς περιοχής. Η γνώση αυτή είναι απαραίτητη για τον καθορισμό των συνθηκών διεξαγωγής πειραμάτων. Τα αποτελέσματα από τους δύο τύπους αντιδραστήρων, δεν παρουσίασαν διαφορές στους χρόνους επαγωγής γεγονός το οποίο υποδεικνύει την αυξημένη σημασία της πυρηνογένεσης και την μικρότερη σημασία της ρευστοδυναμικής του συστήματος. Στους δύο τύπους αντιδραστήρων μελετήθηκε ο ετερογενής σχηματισμός του στρουβίτη σε συνθήκες σταθερού pH 6.50, σε σταθερά υπέρκορα διαλύματα συνθετικού αποβλήτου, χρησιμοποιώντας ως φύτρα για την εκκίνηση της κρυσταλλικής ανάπτυξης, quartz, άμμο και στρουβίτη. Με υπόστρωμα quartz, παρατηρήθηκε μείωση του ρυθμού καταβύθισης αυξανομένης της ποσότητας τόσο σε αντιδραστήρα batch όσο και σε FBR, λόγω της επιβραδυντικής δράσης των πυριτικών ιόντων. Με υπόστρωμα άμμου, παρατηρήθηκε υπερδιπλάσια αύξηση του ρυθμού καταβύθισης για τη διπλάσια ποσότητα φύτρων, το οποίο συνηγορεί στην υπόθεση της δευτερογενούς πυρηνογένεσης. Τα μεγαλύτερα ποσοστά ανάκτησης φωσφόρου της τάξεως ~40% και καταβύθισης στρουβίτη από 70-100% είχαμε σε αντιδραστήρα ρευστοποιημένης κλίνης με υπόστρωμα στρουβίτη. Η χρήση υποστρώματος άμμου είχε αποτελέσματα παραπλήσια με τα αντίστοιχα τα οποία ελήφθησαν με την χρησιμοποίηση φύτρων κρυσταλλικού στρουβίτη. Η εισαγωγή σωματιδίων quartz στα υπέρκορα διαλύματα για την δημιουργία πυρήνων κρυστάλλωσης στρουβίτη είχε ως αποτέλεσμα την συγκριτικά μικρότερη απομάκρυνση φωσφόρου και κρυστάλλωση στρουβίτη. Σε λιγότερα από 700min λειτουργίας των αντιδραστήρων, στα υπέρκορα διαλύματα στα οποία είχαν εισαχθεί φύτρα στρουβίτη, η καταβυθιζόμενη ποσότητα στρουβίτη ήταν η μέγιστη δυνατή. Συγκρίσιμα αποτελέσματα ελήφθησαν με την εισαγωγή άμμου στα υπέρκορα διαλύματα. Το καταβυθιζόμενο στερεό χαρακτηρίστηκε με μεθόδους περίθλασης ακτίνων-X και ηλεκτρονική μικροσκοπία σάρωσης. Στα πειράματα batch, το καταβυθιζόμενο στερεό ήταν στρουβίτης, ενώ στα FBR σε υπόστρωμα 20g quartz σε χαμηλό υπερκορεσμό καταβυθίστηκε μικρή ποσότητα φωσφορικού μαγνησίου και σε υπόστρωμα 5g στρουβίτη σε υπερκορεσμό Ω=1.65 παρατηρήθηκε μικρή ποσότητα newberyite. / Phosphorus is one of the main components in the municipal wastewater, which can lead to problems such as eutrophication in the water reservoirs. The known reserves of phosphorus rocks are decreasing because of the high worldwide demands. Thus, it is necessary to recycle phosphorus from wastewater. Τhe crystallization of struvite is An attractive and new alternative method for phosphorus recovery. Struvite may be used as a slow-release fertilizer because of its relatively low solubility and the presence of both ammonia and phosphorus which through dissolution nutrients available to plants. In the present work, two types of reactors, a fluidized bed reactor (FBR) and a stirred tank reactor were used for the investigation of phosphorus recovery in synthetic wastewater at pΗ 6.50, 25οC. The stoichiometric molar ratio at the constituent ions was 1:1:1 through out the experiments of the present work. The extent of struvite precipitation depends on the solution supersaturation with respect to the precipitating solid, the temperature and the presence of foreign ions or substrates in the solution. The spontaneous precipitation of struvite was studied in both types of reactors at a constant pH 6.50 in order to determine the metastable zone width. This provided knowledge of the stable supersaturated solutions domain where heterogenous nucleation experiments can be done, in order to evaluate nucleation experiments can be done, in order to evaluate the relative ability of substrates to induce the crystallization of struvite. For the two type’s reactors, no significant differences were measured for the induction time, preceding precipitation. This suggested that hydrodynamics is not very important for the conditions of the present work. The heterogeneous formation of struvite was investigated at constant supersaturation and of pH in synthetic wastewater in both types of reactors. The seeds included quartz, sand and synthetic struvite. A decrease in the rate of struvite precipitation was found in both reactors with the use of quartz seeds due to the retardation effect of silicon ions. The use of sand seeds increased the rate of precipitation, while increasing the amount of substrate, resulted in a disproportionate increase at the respective rates of precipitation, suggesting a secondary nucleation process. Phosphorus recovery reached almost 40% and precipitation of struvite from 70 to 100% in the FBR filled with struvite. Sand gave similar results with struvite. The recovery of phosphorus and precipitation with quartz seeds were low, perhaps because of the inhibition effect of the silicon ions. Experiments, in which struvite seeds were used to seed supersaturated solutions, resulted in the precipitation the maximum amount of struvite in less than 700min. The experiments with sand seeds were quite close from the previous experiments especially in high supersaturation values. Finally, the precipitated solid characterized with XRD and SEM. In the batch series, the precipitated solid was struvite but for the FBR experiments a small amount of magnesium phosphate, for supersaturation Ω= 1.65 with 20g quartz seeds and a small amount of newberyite for 5g struvite seeds in supersaturation value 1.65, were obtained. These findings suggested that the problem is complex and kinetic stabilization of metastable mineral phases may be formed at very specific conditions.

Les minerais d’uranium sont généralement peu concentrés avec des teneurs en uranium inférieures à 1%. Pour éviter le transport inutile de tonnages importants sur de longues distances, des opérations de purification et de concentration s’effectuent à proximité immédiate des sites miniers. Après purification, l’uranium est précipité pour conduire à un concentré solide appelé couramment « Yellow-Cake » et contenant entre 70 et 76% d’uranium. Cette thèse apporte une contribution à l’étude du procédé de précipitation du Yellow-Cake, sous forme de peroxyde d’uranium, en réacteur à lit fluidisé. Afin de mieux comprendre tous les mécanismes mis en jeu au cours de la précipitation, nous avons développé des méthodes permettant de mettre au point un modèle de solubilité, de compléter les données cinétiques et de proposer un modèle décrivant le procédé de précipitation en réacteur à lit fluidisé. Les cinétiques de nucléation et de croissance cristalline ont été déterminées par Planteur (2013). L’identification de la loi cinétique d’agglomération consiste en la détermination du noyau d’agglomération en fonction des paramètres influençant le mécanisme d’agglomération. Plus précisément, dans le cas du peroxyde d’uranium, le mécanisme d’agglomération est caractérisé par un noyau d’agglomération constant par rapport à la taille des particules, mais proportionnel à la vitesse de croissance cristalline (ordre 1 vis-à-vis de la sursaturation) et une vitesse d’agglomération freinée significativement par une augmentation du taux de cisaillement. L’étude expérimentale du procédé de précipitation du peroxyde d’uranium en réacteur à lit fluidisé a porté sur l’influence des conditions opératoires sur la qualité du produit final obtenu : vitesse d’agitation, capacité du réacteur et teneur en sulfate. À partir des données expérimentales obtenues en réacteur à lit fluidisé sur une installation pilote, un modèle de réacteur parfaitement mélangé avec séparation de la phase solide (MSSPR) est développé avec succès pour le procédé de précipitation du peroxyde d’uranium. Le modèle proposé peut ensuite être mis à profit pour dimensionner les précipitateurs à lit fluidisé du type MSSPR / Currently exploited uranium deposits contain less than 1% of uranium. Once uranium ore has been extracted, it is transported to a processing plant. Purification and concentration are required in order to reduce the cost of uranium transportation. The precipitation of uranium present inside mill leach solutions produces a solid known as yellow cake. This precipitate contains around 75% uranium. This PhD thesis deals with the yellow cake precipitation process in a fluidized-bed reactor. The process produces uranium peroxide. We develop methods for studying the kinematic mechanisms that take place during the precipitation process. We provide a global model of the uranium peroxide precipitation process in a fluidized-bed reactor. Planteur (2013) studies the kinematics of uranium peroxide nucleation and crystal growth. His thesis work presents a parametric study that quantifies the influence of operating parameters on the agglomeration mechanism. The uranium peroxide agglomeration kernels are found to be particle size-independent, directly proportional of the crystal growth rate, and inversely proportional to the average shear rate. Our experiment stresses the influence of key operating parameters on the yellow cake precipitation in a fluidized-bed reactor. We investigate the effects of stirring speed, feed flow, and sulfate concentration on the uranium peroxide precipitation. We use our experimental results for modeling the precipitation process. We propose a model called Mixed Suspension Separated Product Removal (MSSPR). The successful application of this model reveals its potential for sizing fluidized-bed reactors at the industrial scale

The research determined that the improved heat transfer characteristics of a fluidized bed reactor (FBR) will allow the use of cobalt catalyst for high temperature Fischer-Tropsch synthesis (HTFT). Cobalt was loaded onto a gamma alumina support, the catalyst was characterized using TPR, BET/BJH, XRD, and PSA to track changes in the catalyst morphology. The reactor was characterized to determine the minimum fluidization velocity and the maximum velocity prior to entering lean phase fluidization with pneumatic transport of the catalyst. The highest minimum fluidization velocity was found to be about 2800 sccm, there was no maximum velocity found for the reactor setup. Once characterized, the reactor was operated at pressures of 145, 217.6, and 290.1 psig, a syngas flow rate of 4000 sccm, and at temperatures of 330 and 350 °C. The optimal conditions found in this study were 330 °C and 217 psig. At these conditions CO conversion was 83.53 % for a single pass. Methane, CO2, and light gases (C2 - C4) selectivities were at low rates of 31.43, 5.80, and 3.48 % respectively. Alcohol selectivity at these conditions was non-existent. The olefin and wax selectivities were the lowest of the data set at 7.05 and 3.18 % respectively. Liquid transportation fuels selectivity was the highest at 56.11 %.

Este trabalho teve como objetivo avaliar o desempenho de um reator anaeróbio de leito fluidificado na degradação da vinhaça de cana-de-açúcar, sob condições mesofílicas. Ensaios batelada foram realizados a diferentes concentrações, visando avaliar a degradação do substrato pela biomassa anaeróbia e obtenção de parâmetros cinéticos. Vinhaça diluída a valores de DQO de 1984 mg/L, 2827 mg/L, 3800 mg/L, 6354 mg/L, 7395 mg/L, 10705 mg/L e 15872 mg/L foi utilizada nos experimentos, mostrando reduções de 67% em 192 horas, 75% em 358 horas, 81% em 408 horas, 80% em 480, 72% em 504 horas, 76% em 840 horas e de 71% em 1080, para essas concentrações, respectivamente. A reação ocorrida nos reatores foi analisada como sendo de ordem zero, com valor médio da constante de reação de 10,4 mg/L.h. Testes com partículas de poliamida, poliestireno e nylon foram realizados, objetivando a escolha da melhor partícula em termos de formação e desenvolvimento de biofilme para posterior uso no reator. As três partículas mostraram-se favoráveis à adesão e colonização de microrganismos. O reator anaeróbio de leito fluidificado foi inoculado com lodo proveniente de reator UASB, que tratava água residuária de abatedouro de aves. O volume do reator era de 770 cm3, operando com tempo de detenção hidráulica de 24 h. A partícula utilizada como material suporte foi poliestireno. O tempo de operação do reator foi de 122 dias, sendo aplicada vinhaça diluída a valores de DQO que variaram de 1009 mg/L a 15874 mg/L e COVa de 1,0 Kg/m3.d a 15,9 Kg/m3.d, apresentando resultado de remoção de DQO médio de 51% a 70% e COVrv de 0,5 Kg/m3.d a 7,9 Kg/m3.d. Observações microscópicas em MEV, mostraram boa adesão microbiana nas partículas de poliestireno, em todas as fases do reator. / This work had as objective evaluates the efficiency of a anaerobic fluidized bed reactor for vinasse degradation under mesophilic conditions. Batch tests seeking to evaluate the degradation of the substratum for the anaerobic biomass and obtaining kinetic parameters were accomplished to different concentrations. Diluted vinasse to values of 1984 mg/L, 2827 mg/L, 3800 mg/L, 6354 mg/L, 7395 mg/L, 10705 mg/L and 15872 mg/L of COD was used in the experiments showing reductions of 67% in 192 hours, 75% in 358 hours, 81% in 408 hours, 80% in 480, 72% in 504 hours, 76% in 840 hours and of 71% in 1080, for those concentrations, respectively. The reaction happened in the batch reactors it was analyzed as being of order zero, with medium value of 10,4 mg/L.h for the constant of reaction. Tests with polyamide particles, polystyrene and nylon were accomplished, aiming at the choice of the best particle in formation terms and biofilme development for subsequent use in the reactor. The three particles were shown favorable to the adhesion and colonization of microorganisms. The fluidized bed reactor was inoculated with sludge from reactor UASB treating effluent frompoultry slaughterhouse. The volume of the reactor was of 770 cm3, operating with hydraulic detention time of 24 h. Polystyrene particles were used as material support. The reactor was operated for 122 days, being applied diluted vinasse to values of COD 1009 mg/L ranging to 15874 mg/L and organic loading rate (OLR) of 1,0 Kg/m3.d to 15,9 Kg/m3.d, presenting efficiency COD removal of 51% - 70% and OLR removal of 0,5 Kg/m3.d - 7,9 Kg/m3.d. Microscopic observations in MEV showed good microbial adhesion in the particles of polystyrene, in all the phases of the reactor.

Orientador: Caio Glauco Sanchez / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-07T01:30:03Z (GMT). No. of bitstreams: 1 Pellegrino_Roberto_M.pdf: 5673705 bytes, checksum: ab5152461f33f423ca032ca41d02c786 (MD5) Previous issue date: 2006 / Resumo: O presente trabalho aborda a influência da adição de vapor d¿água no rendimento do gás combustível e na remoção de H2S do carvão mineral misturado com dolomita e gaseificado em reator de leito fluidizado. Para isso foi necessária a construção de um gaseificador de 0,2 m de diâmetro interno que foi operado sob pressão atmosférica utilizando ar e vapor como agentes fluidizantes. Na primeira etapa deste estudo, verificou-se o funcionamento de todos os componentes do gaseificador e estabeleceu-se as condições de operação. Em uma segunda etapa, fez-se a introdução de vapor e avaliou-se sua influência na formação dos gases gerados. Posteriormente, adicionou-se ao combustível a dolomita como agente adsorvedor e verificou-se seu efeito juntamente com o vapor na remoção do H2S. Nas condições estudadas, observou-se que quando se adiciona vapor, o teor de H2S gerado tende a aumentar consideravelmente atingindo valores de até 2367 ppm. Utilizando-se dolomita totalmente calcinada na razão molar Ca/S = 2, e 10 e 20 % de vapor a porcentagem de remoção de H2S situou-se em torno de 40%. Porém, quando se aumenta a razão Ca/S para 4 e vapor a 20%, os valores de remoção de H2S obtidos foram de aproximadamente 80% / Abstract: The present work deals with the influence of water steam addition in the calorific value of combustible gas resulting from gasification of mineral coal and dolomite mixture, and in the H2S removal. The experiments were carried out in a fluidized bed reactor with 0,2 m of inner diameter, operated at normal atmosphere pressure, using air and water steam as fluidizing agents. In the first stage of this study, working conditions of all components was verified and operating parameters were established. Then water steam was introduced in reactor and its influence on formed gases was evaluated. In a sequence, dolomite was added to the coal as adsorbing agent and its effect on H2S removal was also followed. It has been observed for the experimental conditions of this work an increasing H2S when water steam is introduced in the reactor reaching values of 2367 ppm. By rising calcined dolomite, in the molar ratio of Ca/S = 2, plus 10 and 20% of steam, a 40% of H2S removal was observed. However for a Ca/S = 4 molar ratio and 20% of steam, H2S removal increased to 80% / Mestrado / Termica e Fluidos / Mestre em Engenharia Mecânica

O objetivo deste estudo foi avaliar o efeito da adição de alcalinidade, da concentração da glicose e da taxa de carregamento orgânico na produção de hidrogênio e ácidos orgânicos em reator anaeróbio de leito fluidificado (RALF), contendo argila expandida (2,8 - 3,35 mm) como material suporte para adesão microbiana. Foram utilizados oito reatores idênticos, sendo quatro deles operados sem adição de alcalinidade, e com concentração de glicose de 2000, 4000, 10000 e 25000 mg/L, respectivamente. Outros quatro reatores operados com adição de alcalinidade, e com as mesmas concentrações de glicose cada um. Os reatores foram inoculados com lodo anaeróbio pré-tratado termicamente, operado com tempo de detenção hidráulica (TDH) decrescente de 8 h a 1 h à temperatura controlada de 30°C. Foi constatada produção volumétrica de hidrogênio máxima de 1,58 L/h.L, para o reator operado com 10000 mg/L de glicose com adição de alcalinidade (R10CA) e um rendimento máximo de 2,52 mol \'H IND.2\'/mol glicose, para o reator operado com 4000 mg/L de glicose com adição de alcalinidade (R4CA). O biogás produzido foi composto de \'H IND.2\' e \'CO IND.2\'. Em ambos os reatores, o conteúdo de hidrogênio aumentou com a redução do TDH de 8 h para 1 h, alcançando valor máximo de 77%, para o reator operado com 4000 mg/L sem adição de alcalinidade (R4SA). Os reatores operados com altas concentrações de glicose produção de hidrogênio, o qual predominou o ácido acético e butírico. Neste mesmo reator, o rendimento da produção de hidrogênio foi superior aos outros reatores. As análises de clonagem e sequenciamento do consórcio bacteriano revelaram semelhanças com Clostridium, Klebsiella, Enterobacter e bactérias não cultivadas. / This study evaluated the effect alkalinity addition, glucose concentration and organic loading rate in the hydrogen production and organic acids in an anaerobic fluidized bed reactor (AFBR), containing expanded clay (2.8 - 3,35 mm) as support material for microbial adhesion. We used eight identical reactors, four of them operated without the addition of alkalinity, and concentration of glucose in 2000, 4000, 10000 and 25000 mg/L, respectively. Another four reactors operated with the addition of alkalinity, and with the same concentrations of glucose each. The reactors were operated with hydraulic retention times (HRT) ranging from 8 h at 1 h, and temperature of 30°C. It has been found for hydrogen production rate maximum 1.58 L/h.L for the reactor operated with 10000 mg/L glucose with the addition of alkalinity (R10CA) and a maximum yield of 2.52 mol \'H IND.2\'/mol glucose to the reactor operated with 4000 mg/L glucose with the addition of alkalinity (R4CA). The biogas produced was composed of \'H IND.2\' and \'CO IND.2\'. In both reactors, the hydrogen content increased with the reduction of HRT of 8 h at 1 h, reaching a maximum of 77% for the reactor operated from 4000 mg/L without added alkalinity (R4SA). The reactors operated with high glucose concentrations (10000 mg/L and 25000 mg/L) had higher proportions of solvents such as soluble metabolites. There was a linear correlation between the hydrogen production rate and organic loading rate in all reactors. The yield, the hydrogen production rate and distribution of soluble metabolites in both reactors, were influenced by the glucose concentration. The reactor operated with 4000 mg/L and addition of alkalinity, presented the most favorable distribution of soluble metabolites to hydrogen production, which was predominant acetic and butyric acid. In the same reactor, the hydrogen yield was higher than other reactors. The cloning and sequencing analysis bacterial consortium revealed the presence of Clostridium, Klebsiella, Enterobacter and uncultivated bacteria.

Orientador: Caio Glauco Sánchez / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-23T18:32:48Z (GMT). No. of bitstreams: 1 Vissotto_JoaoPaulo_M.pdf: 17443827 bytes, checksum: 1532a467facbbea36dcaa47864ef9b7d (MD5) Previous issue date: 2013 / Resumo: Este trabalho aborda o estudo da cogaseificação de dois tipos de resíduos de biomassas (serragem de pinus e lodo de esgoto sanitário esgoto sanitário e industrial da cidade de Americana - SP) com o objetivo de comprovar experimentalmente os efeitos sinérgicos de misturas dessas biomassas. O lodo de esgoto não tem PCI suficiente para sustentar o processo de gaseificação sozinho, assim sua mistura com a serragem possibilita a realização do processo, além da diluição de possíveis contaminantes. Na caracterização das biomassas escolhidas, foram determinados os valores de PCI para o pinus de 17,19 MJ.kg-1 e para o lodo de 11,48 MJ.kg-1. Os teores de voláteis foram de 89,69 % e 58,32 % respectivamente. Os ensaios foram realizados no gaseificador do Laboratório de Combustão e Gaseificação do Departamento de Engenharia Térmica e de Fluídos da Faculdade de Engenharia Mecânica da UNICAMP, que é um reator de leito fluidizado borbulhante. Durante os ensaios de gaseificação foram selecionados dois fatores de ar para gaseificação exclusiva de pinus (0,30 e 0,50). Os valores de poder calorífico do gás produto foram calculados a partir da concentração do gás obtido, determinado por cromatografia gasosa, sendo os valores de 3,63 ± 0,4 MJ. Nm-3 e 1,92 ± 0,2 MJ. Nm-3 respectivamente. A adição de lodo para os ensaios de cogaseificação foram à razão de 25 % em massa, base seca, para o fator de ar de 0,30, pois nesse fator de ar ocorreu o melhor PCI do gás e o melhor rendimento a frio do gaseificador com gaseificação de pinus puro (37,1%). O valor de PCI para o gás produto da cogaseificação foi de 2,62 ± 0,67 MJ. Nm-3. O rendimento médio do gaseificador caiu para 29,3% / Abstract: This work aims to study the cogasification of two types of biomass residues (sawdust pine and sanitary and industrial sewage sludge from Americana City - São Paulo State) in order to experimentally demonstrate the synergistic effects of mixtures of these biomasses .The LHV of the sewage sludge is not enough to sustain the gasification process alone, so its mixture with sawdust allows the realization of the process and the dilution of possible contaminants. In the characterization of biomasses, the LHV values were for pine 17.19 MJ.kg-1 and for the sludge 11.48 MJ.kg-1. The content of volatiles were 89.69 % and 58.32 % respectively. Experiments were performed in the gasifier of The Combustion and Gasification Laboratory, Department of Thermal Engineering and Fluid Mechanics of the Faculty of Mechanical Engineering , UNICAMP , which is a bubbling fluidized bed reactor. During the gasification tests, two air ratio were selected for gasification of pine alone (0.30 and 0.50). The low heating value of the product gas was calculated from the gas concentration, determined by gas chromatography, with values of 3.63 ± 0.4 MJ.Nm-3 and 1.92 ± 0.2 MJ.Nm-3 respectively. The addition of sewage sludge for cogasification was in the rate of 25 % on dry basis, for 0.30 air ratio, because in this air ratio occurred the best LHV in the gas and the best performance of gasifier with pure pine ( 37.1 %). The average value of LHV for gas product of cogaseificação was 2.62 ± 0.67 MJ . Nm-3. The average efficiency of the gasifier fell to 29.3 % / Mestrado / Termica e Fluidos / Mestre em Engenharia Mecânica

Groundwater (GW) accounting for most of the freshwater available around the World, finding sustainable techniques to depollute it is of crucial importance for safe drinking water supply. The extensive use of fertilizers in the agriculture, as well as other anthropogenic activities, are contributing to the excessive nitrate levels in some aquifers. These levels need to be reduced to obtain potable water. Bioelectrochemical systems (BES), using microorganisms to catalyze a desired electrochemical reaction, recently proved to be a very promising technology for water remediation. Groundwater denitrification using Microbial Electrolysis Cell (MEC) needs to be improved for further scaled-up on-site system. The advantages conferred by fluidized bed reactor (FBR), as well as the outstanding electrochemical properties of reduced graphene oxide (rGO), are two potential enhancements of such bioelectrochemical denitrification system that were investigated in this thesis. Some essential parameters could be determined during the preliminary steps' experiments. The fluidization trials gave us a clear insight that Coconut-based Activated Carbon (CAC) particles were resistant carrier particles, nicely fluidized within a 39.27cm3 circular cathodic chamber for a flow rate ranging between 450ml/min to 590ml/min. For the same flow rate of 500ml/min, we could obtain CAC particles fluidization for the upstream fluidized configuration, and still bed particles for the fixed bed downstream configuration, which would be very useful for later unbiased comparison. The denitrifying bacteria showed during their enrichment, a nitrate removal rate of up to 1.986ppm NO3-N/h in serum bottles, with an average of 0.38ppm NO2-N/h accumulation. The parallel running of fixed bed versus fluidized bed denitrifying reactor in order to compare their denitrification performances, was planned, but could not be performed due to COVID-19. The graphene oxide (GO) batch experiments showed a good biocompatibility between GO/rGO and our autotrophic denitrifying bacteria. A change of morphology within about 20 hours was observed, probably suggesting the reduction of GO to rGO by the bacteria. During a first test, the presence of GO led to a 2.7 folds less efficient denitrification performance as compared with the GO/rGO-free condition, likely due to the competition between nitrate and GO for being reduced. However, the denitrification rate in presence of GO/rGO increased up to 1.873ppm NO3-N/h after the second pulse of groundwater and flush with H2/CO2 gas, which is almost 2.3 folds higher than initially in the same condition. This suggests that GO needs some time to get fully reduced to rGO, and the denitrification rate might reach the same or higher levels as in the GO/rGO-free conditions, when GO is fully reduced. Improved denitrification would indicate that rGO facilitates the electron transfer between bacteria and nitrate, as it can be expected from its electrochemical properties previously studied. This would be worth being investigated in the scope of a longer experience. / Grundvatten (GW) som står för det mesta av det sötvatten som finns tillgängligt runt om i världen och att hitta hållbara tekniker för att förorena det är av avgörande betydelse för en trygg dricksvattenförsörjning. Den omfattande användningen av gödselmedel i jordbruket, liksom andra antropogena aktiviteter, bidrar till de överdrivna nitratnivåerna i vissa vattenfiskare. Dessa nivåer måste sänkas för att erhålla dricksvatten. Bioelektrokemiska system (BES), med användning av mikroorganismer för att katalysera en önskad elektrokemisk reaktion, visade sig nyligen vara en mycket lovande teknik för sanering av vatten. Grundvatten denitrifikation med hjälp av Microbial Electrolysis Cell (MEC) måste förbättras för att ytterligare skala upp systemet på plats. Fördelarna med fluidiserad bäddreaktor (FBR) såväl som de enastående elektrokemiska egenskaperna hos reducerad grafenoxid (rGO) är två potentiella förbättringar av ett sådant bioelektrokemiskt denitrifikationssystem som undersöktes i denna avhandling. Vissa väsentliga parametrar kan bestämmas under de preliminära stegens experiment. Fluidiseringsstudierna gav oss en klar insikt om att kokosnötbaserade aktiverade kolpartiklar (CAC) -partiklar var resistenta bärarpartiklar, trevligt fluidiserade i en cirkulär katodisk kammare på 39,27 cm3 för en flödeshastighet mellan 450ml/min till 590ml/min. För samma flödeshastighet på 500ml/min kunde vi få CAC-partikelfluidisering för uppströms fluidiserad konfiguration och stillbäddspartiklar för den fixerade bädden nedströms konfiguration, vilket skulle vara mycket användbart för senare opartisk jämförelse. De denriffriserande bakterierna visade under deras anrikning en nitratborttagningshastighet av upp till 1,986 ppm NO3-N/h i serumflaskor, med ett genomsnitt på 0,38 ppm NO2-N / h ackumulering. Den parallella körningen av denitrifierande reaktorn med fast bädd kontra fluidiserad bädd för att jämföra deras denitrifikationsprestanda planerades, men kunde inte utföras på grund av COVID-19. Diagramexperimenten av grafenoxid (GO) visade en god biokompatibilitet mellan GO/rGO och våra autotrofiska denitrifierande bakterier. En förändring av morfologin inom cirka 20 timmar observerades, vilket antagligen antydde att bakterierna minskade GO till rGO. Under ett första test ledde närvaron av GO till 2,7 gånger mindre effektiv denitrifikationsprestanda jämfört med GO/rGO-fritt tillstånd, troligtvis på grund av konkurrensen mellan nitrat och GO för att ha minskat. Denitrifikationsgraden i närvaro av GO/rGO ökade emellertid upp till 1,873 ppm NO3-N/h efter den andra grundvattenspulsen och spolades med H2/CO2-gas, vilket är nästan 2,3 gånger högre än ursprungligen i samma tillstånd. Detta antyder att GO behöver lite tid för att helt reduceras till rGO, och denitrifikationsgraden kan nå samma eller högre nivåer som i GO/rGO-fria förhållanden, när GO är helt reducerad. Förbättrad denitrifikation skulle indikera att rGO underlättar elektronöverföring mellan bakterier och nitrat, som det kan förväntas av dess elektrokemiska egenskaper som tidigare studerats. Detta skulle vara värt att undersökas inom ramen för en längre upplevelse.

To release energy from chemically stored energy in the biomass was the new investigation in recent years. Utilizing of biomass for this purpose occur in two different ways, directly by burning (combustion) the biomass and indirectly by pyrolysis process which will convert the biomass to three main products, bio- tar, bio- char and synthetic gas. Biomass contains different amount of inorganic compound, especially alkali metals which causes some diverse impacts on combustion, pyrolysis and gasification process such as corrosion, agglomeration and fouling problems. This project aims to investigate the effect of K2CO3 on the pyrolysis and gasification processes of three different types of fuel; wood pellets, forest residue pellets and synthetic waste pellets at three different temperatures, 750 °C, 850 °C and 900 °C respectively. The purpose of this work to study and clarify the influence of K2CO3 on char yield, tar yield and tar compositions and the gasification rate and the reactivity of different fuels char. The pyrolysis process was carried out in a fluidized bed reactor during 2 minutes and the products were tar, char and synthetic gas. In this project interested in char and tar only. Char yield calculated and the results shows the char yield increase with increasing of [K2CO3]. While the tar analysis carried on GC- MS instrument at HB to study the tar yield and compositions. The results showed that potassium carbonate has not so much effect on tar yield and its composition. The last part was gasified the char in TGA with steam and CO2 as oxidizing media to study the influence of [K2CO3] on gasification rate and the reactivity of char samples at different temperatures. The result showed the [K2CO3] has inhibitory effect on gasification rate and the reactivity.