Η φωτοκαταλυτική διάσπαση του νερού προς παραγωγή υδρογόνου με χρήση φωτοκαταλύτη διοξειδίου του τιτανίου (TiO2) μελετήθηκε με χρήση τεχνητής ηλιακής ή ορατής ακτινοβολίας Βρέθηκε ότι ο αρχικός ρυθμός της αντίδρασης αυξάνεται σημαντικά με την προσθήκη μικρών ποσοτήτων Pt στην επιφάνεια του ημιαγωγού. Στον καταλύτη αυτό, μελετήθηκε η επίδραση του pH καθώς και της θερμοκρασίας του αιωρήματος στην φωτοκαταλυτική παραγωγή υδρογόνου. Τα αποτελέσματα των πειραμάτων έδειξαν ότι τόσο η αύξηση του pH όσο και η αύξηση της θερμοκρασίας έως τους 800C οδηγούν σε ενίσχυση του ρυθμού παραγωγής. Ο ρυθμός μπορεί να αυξηθεί περαιτέρω και να διατηρηθεί σε υψηλά επίπεδα για μεγάλους χρόνους ακτινοβόλησης, αν στο υδατικό αιώρημα προστεθεί ποσότητα «δότη ηλεκτρονίων» σε κατάλληλη συγκέντρωση. Πρόκειται για οργανικές ενώσεις (χρωστικές, αλκοόλες, σάκχαρα κ.α.) που απαντώνται σε απόβλητα χημικών βιομηχανιών, οι οποίες δρουν σαν «θυσιαζόμενες» ενώσεις. Ο ρόλος τους είναι η γρήγορη απομάκρυνση των φωτοπαραγόμενων οπών (ριζών υδροξυλίου) ή/και του φωτοπαραγόμενου οξυγόνου, κατά έναν μη αντιστρεπτό τρόπο, εμποδίζοντας έτσι την επανασύνδεση ηλεκτρονίου-οπής ή/και την αντίστροφη αντίδραση Ο2-Η2 Όταν επιτυγχάνεται πλήρης οξείδωση της οργανικής ένωσης (και των ενδιαμέσων της αντίδρασης) σε διοξείδιο του άνθρακα, το οξυγόνο δεν μπορεί πλέον να απομακρυνθεί από την επιφάνεια του φωτοκαταλύτη, με αποτέλεσμα ο ρυθμός παραγωγής Η2 να μειώνεται στα επίπεδα του ρυθμού μόνιμης κατάστασης, που επιτυγχάνεται απουσία «θυσιαζόμενης» ένωσης από το διάλυμα. Οι συνολικά παραγόμενες ποσότητες Η2 και CO2 είναι ευθέως ανάλογες με την ποσότητα του δότη ηλεκτρονίων που αρχικά προτίθεται στο διάλυμα. Επομένως, η παραγωγή υδρογόνου από την φωτοκαταλυτική διάσπαση του νερού με χρήση «θυσιαζόμενων» ενώσεων αποτελεί μια πολλά υποσχόμενη διεργασία καθώς, παράλληλα με τη δυνατότητα παραγωγής υδρογόνου μέσω της ηλιακής ακτινοβολίας, μπορεί να χρησιμοποιηθεί για την ταυτόχρονη αποικοδόμηση οργανικών ρύπων που απαντώνται σε υγρά βιομηχανικά απόβλητα. / The production of hydrogen from aqueous TiO2 suspensions illuminated with UV/vis or visible light has been examined It has been found that deposition of Pt (0.5 wt.%) on the semiconductor surface results in an increase of the H2 production rate, which goes through a maximum with time of irradiation and then drops to steady-state values comparable to those obtained over bare TiO2. Both, maximum and steady-state rates obtained over Pt/TiO2 suspensions were found to increase with increasing solution pH and temperature. Addition of small quantities of electron donors (such as dyes, alcohols and sugars) in solution results in significantly enhanced rates of H2 production. Results are explained by considering that organic compounds act as sacrificial agents, which become progressively oxidized toward CO2 by consuming photogenerated holes and/or oxygen. This results in decreased rates of electron-hole recombination and oxygen-hydrogen back reaction and, concomitantly, in increased H2-production rates. The rate of photoinduced hydrogen production depends strongly on the concentration of the sacrificial agent employed and to a lesser extent on solution pH and temperature. When complete mineralization of the sacrificial agent is achieved, photogenerated oxygen can no longer be removed from the photocatalyst surface and the H2-production rate drops to steady-state values, comparable to those obtained in the absence of the organic compound in solution. The amounts of carbon dioxide and “additional” hydrogen produced depend on the nature of the organic additive and are directly proportional to its initial concentration in solution. Quantification of results shows that the overall process may be described as “photoinduced reforming of organic compounds at room temperature”. It is concluded that mineralization of organic pollutants, which are common waste products of biomass processing industries, can be achieved with simultaneous production of H2 fuel. The process may provide an efficient and cost effective method for cleaning up waste streams.

Photocatalytic processes over semiconducting oxide surfaces have attracted worldwide attention aspotentially efficient, environmentally friendly and low cost methods for water/air purification as well as forrenewable hydrogen production. However, some limitations to achieve high photocatalytic efficiencies havebeen found due to the fast recombination of the charge carriers. Development of heterostucture photocatalystsby depositing metals on the surface of semiconductors or by coupling two semiconductors with suitable bandedge position can reduce recombination phenomena by vectorial transfer of charge carriers. To draw newprospects in this domain, three different kinds of heterostructures such as n-type/n-type semiconductor(SnO2/ZnO), metal/n-type semiconductor (RuO2/TiO2 and RuO2/ZnO) and p-type/n-type semiconductor(NiO/TiO2) heterojunction nanomaterials were successfully prepared by solution process. Their composition,texture, structure and morphology were thoroughly characterized by FTIR, X-ray diffraction (XRD), Ramanspectroscopy, transmission electron microscopy (TEM) and N2 sorption measurements. On the other hand, asuitable combination of UV-visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy(XPS) and ultraviolet photoemission spectroscopy (UPS) data provided the energy band diagram for eachsystem. The as-prepared heterojunction photocatalysts showed higher photocatalytic efficiency than P25 TiO2for the degradation of organic dyes (i.e. methylene blue and methyl orange) and the production of hydrogen.Particularly, heterostructure RuO2/TiO2 and NiO/TiO2 nanocomposites with optimum loading of RuO2 (5 wt %)and NiO (1 wt %), respectively, yielded the highest photocatalytic activities for the production of hydrogen.These enhanced performances were rationalized in terms of suitable band alignment as evidenced by XPS/UPSmeasurements along with their good textural and structural properties. This concept of semiconductingheterojunction nanocatalysts with high photocatlytic activity should find industrial application in the future toremove undesirable organics from the environment and to produce renewable hydrogen.

Το αντικείμενο της διδακτορικής διατριβής είναι η σύνθεση, ο χαρακτηρισμός και η μελέτη φωτοευαίσθητων ηλεκτροκαταλυτών TiO2 και η μορφοποίηση τους σε ηλεκτρόδια, τα οποία και μελετήθηκαν ως προς την φωτοηλεκτροχημική παραγωγή υδρογόνου από νερό ή/και οργανικές ενώσεις. Τα ηλεκτρόδια λεπτών υμενίων παρασκευάστηκαν με τη μέθοδο εμβάπτισης – επίστρωσης σε διάλυμα TiO2. Τα ηλεκτρόδια Τιτάνιας ήταν νανοπορώδη και παρουσίαζαν νανοκρυσταλλική δομή ανατάση με μέγεθος σωματιδίων 15 nm. Η μελέτη των ηλεκτροδίων πραγματοποιήθηκε σε φωτοηλεκτροχημικό αντιδραστήρα. Τα αποτελέσματα έδειξαν ότι η φωτοβόληση των ηλεκτροδίων τιτάνιας τα ενεργοποιεί, διεγείροντας ηλεκτρόνια στη ζώνη αγωγιμότητας και δημιουργώντας οπές στη ζώνη σθένους. Για την παραγωγή υδρογόνου ήταν απαραίτητη η επιβολή δυναμικού ή η παρουσία οργανικών ενώσεων στον ηλεκτρολύτη. Ο ρυθμός παραγωγής υδρογόνου βελτιστοποιήθηκε συναρτήσει του πάχους του υμενίου και της συγκέντρωσης των οργανικών ενώσεων στον ηλεκτρολύτη. Συμπερασματικά έχει τεράστιο δυναμικό για εφαρμογή σε φωτοηλεκτροχημικά κελιά καυσίμου για ταυτόχρονο καθαρισμό υδάτων από οργανικούς ρύπους και παραγωγή ενός «καθαρού» καυσίμου, του υδρογόνου. / The object of this thesis is the composition, characterization and the study of photosensitive TiO2 electrocatalysts and their formation in electrodes, which were studied for the photoelectrochemical production of hydrogen from water and/or organic compounds. The thin film electrodes were prepared with the dip - coating method in TiO2 solution. The titania electrodes were nanoporous and nanocrystaline, of anatase phase with particle size 15 nm. The study of electrodes took place in a photoelectrochemical reactor. The results showed that the illumination of the titania electrode activates it, arousing electrons in the conduction band and creating holes in the valence band. For the production of hydrogen, it was necessary to apply potential, or the presence of organic compounds in the electrolyte. The production rate of hydrogen was optimised with respect to the thickness of the film and the concentration of organic compounds in the electrolyte. In conclusion, this method has enormous potential for application in photoelectrochemical fuel cells for simultaneous cleaning of water from organic pollutants and production of “clean” fuel, hydrogen.

L’électrolyse de la vapeur d’eau à haute température (EHT) est une voie permettant de produire de l’hydrogène d’une grande pureté et avec un fort rendement, ceci sans émission de CO2. Un des verrous actuels de cette technologie est la forte surtension associée à la réaction d’oxydation des ions O2- qui se déroule à l’électrode à oxygène (anode). L’objectif de ce travail était de concevoir de nouveaux matériaux d’anode possédant des propriétés de conductivité mixte (i.e. électronique et ionique), dans le but d’obtenir des surfaces de réaction plus importantes afin de diminuer cette surtension. A cet effet, une étude comparative a été réalisée sur huit oxydes (ferrites et nickelates de terres rares). Après synthèse et mise en forme, ces matériaux ont fait l’objet de caractérisations physico-chimiques puis électrochimiques en demi-cellules symétriques sous atmosphère unique afin de déterminer ceux présentant les meilleures propriétés sous courant nul et sous polarisation anodique. Quatre composés de structure dérivée de type K2NiF4 ont ainsi été sélectionnés pour être caractérisés de façon plus approfondie en cellules complètes à électrolyte support en conditions EHT (750 - 850°C). Il a ainsi été possible d’obtenir, pour une tension de cellule de 1,3 V une densité de courant de 0,9 A/cm² à 850°C, soit près de deux fois plus qu’avec une cellule identique comportant comme matériau d’anode un composite commercial optimisé à base de LaMnO3 substitué au strontium. / High temperature steam electrolysis (HTSE) is a way to produce hydrogen with a high purity, with noteworthy efficiency and without CO2 emission. Nowadays, a blocking point concerning this technology is the high overvoltage related to the oxidation of the O2- ions occurring at the oxygen electrode (anode). The aim of this work was to design new anode materials with mixed conducting properties (i.e. electronic and ionic), in order to obtain larger reaction areas and to lessen this overvoltage. In this aim, eight compounds (ferrites and rare earth nickelates) were investigated. After synthesis and shaping, these compounds were characterized using physical, chemical and electrochemical analyses in symmetrical half cells, under single atmosphere, in order to determine which ones have the best properties under zero current and under anodic polarization. Four compounds of structure derived from K2NiF4-type were then selected to be more accurately characterized in complete electrolyte supported cells, under HTSE conditions (750 - 850°C). It was then possible to obtain, for a 1.3 V cell voltage, a current density of 0.9 A/cm² at 850°C, which is nearly two times larger than the one obtained with a same cell including a commercial composite material based on strontium substituted LaMnO3 as anode.

Le contexte de cette thèse est la production du vecteur énergétique hydrogène par thermolyse de la vapeur d’eau consistant en la dissociation de la molécule H2O en oxygène (O) et hydrogène (H). Le dispositif employé est une torche à plasma d’arc non transféré développée au LAEPT. Après l’exposition de la théorie sur la physique des plasmas et la spectrométrie d’émission atomique nécessaire à l’exploitation des mesures, cette thèse présente l’évolution de la torche à plasma ainsi que son environnement nécessitée par la présence de gaz instables et explosifs. Les mesures des différentes grandeurs électriques, hydrauliques et spéctrométriques ont permis la détermination des caractéristiques physique et chimique d’un plasma formé d’un mélange de vapeur d’eau – d’argon. La détermination de grandeurs telles que la température du jet plasma, la conductivité électrique, l’enthalpie massique et la densité électronique, est basée sur la comparaison entre expérimentation et théorie. / The context of this thesis is the production of hydrogen as an energy vector by steam thermolysis consisting in the dissociation of H2O molecule into oxygen (O) and hydrogen (H). The process used is a plasma torch device developed by the LAEPT. After presenting the theory of plasma physics and atomic emission spectroscopy which will help to make the most of the measured realized, this thesis will show the evolution of the plasma torch device and the experimental environment required to work with explosive and unstable gases. Some measurements like electrical, hydraulic and spectroscopy magnitudes made it possible to determine the chemical and physical characteristics of a water vapor – argon plasma. A comparison between experiments and theoretical knowledge will enable to determine the temperature of a flow of plasma, electrical conductivity, enthalpy and the electronic density.

Energy sources usually used are fossil fuels, which are recursosexauríveis and combustion gases responsible for environmental damage generates. For these reasons, it is necessary to identify alternative energy sources that produce less negative impacts. In this scenario, the hydrogen arises as an alternative source of energy, since it is renewable and there's only generation combustion of oxygen and water, and therefore considered a clean fuel. Similarly, the methane is important in decentralised energy generation and contributes to increase the viability of implementing waste treatment processes. The fermentation is a biological process sustainably to produce hydrogen and methane, because you can use as many different types of agro-industrial waste substrate rich in carbs, minimizing the problems caused by the improper disposal of these materials, which can be harmful to the environment. On the above, the objective of this work was to apply agro-industrial residue of coconut processing in anaerobic reactors for biological production of hydrogen and methane, studying the acidogenic phase coupling with metanogênica serial reactors (two-phase system). For development, were used two anaerobic Fluidised bed reactors (RALF) in series, the first being for the biological production of hydrogen from the agro-industrial residue and the second for reusing the effluent of acidogênico first RALF, aiming at the production of methane. The reactors were operated under progressive increase of organic loading rate (TCO), varying the hydraulic detention time (TDH) of operation. For adhesion of microorganisms, employed as materials supports the expanded clay in the reactor for production of hydrogen and the shells of sururu on methane production reactor. It was found that the generation of hydrogen and methane in two-phase system. Higher income and percentage were obtained on biogas in the TDH of 2:00, corresponding to the values of 2.45 mol H2/mol glucose and 33.82%. Already the largest hydrogen production occurred in the TDH of 1:00, it was 0.57 L/h/l. for the production, income and the percentage in methane biogas, highest values were observed in the TDH of 12:00 am such values corresponded, respectively, to 1.56 L/h/L, 0.09 L CH4/g cod and 38.60%. During the operation of the reactors, were observed in all stages, the presence of acetic acid, butyric acid, propionic acid, caproic acid and ethanol. Compared to other systems of anaerobic digestion, two-phase system used in this work showed satisfactory performance parameters. / Fundação de Amparo a Pesquisa do Estado de Alagoas / As fontes energéticas usualmente utilizadas são os combustíveis fósseis, que são recursosexauríveis e cuja combustão gera gases responsáveis por danos ambientais. Por esses motivos, faz-se necessário identificar fontes de energias alternativas que produzam menos impactos negativos. Nesse cenário, o hidrogênio surge como uma fonte alternativa de energia, já que é de origem renovável e na sua combustão há a geração apenas de oxigênio e água, sendo, portanto, considerado um combustível limpo. Similarmente, o metano é importante na geração descentralizada de energia e contribui para aumentar a viabilidade da implementação de processos de tratamentos de resíduos. O processo biológico fermentativo é uma forma sustentável de produzir hidrogênio e metano, pois pode utilizar como substrato diversos tipos de resíduos agroindustriais ricos em carboidratos, minimizando os problemas causados pelo descarte inadequado desses materiais, os quais podem ser nocivos ao meio ambiente. Diante do exposto, o objetivo deste trabalho foi aplicar o resíduo agroindustrial do processamento de côco em reatores anaeróbios para a produção biológica de hidrogênio e metano, estudando o acoplamento da fase acidogênica com a metanogênica em reatores em série (sistema de duas fases). Para o desenvolvimento, foram usados dois reatores anaeróbios de leito fluidificado (RALF) em série, sendo o primeiro para a produção biológica de hidrogênio a partir do resíduo agroindustrial e o segundo para reaproveitar o efluente acidogênico do primeiro RALF, objetivando a produção de metano. Os reatores foram operados sob aumento progressivo da taxa de carregamento orgânico (TCO), variando o tempo de detenção hidráulica (TDH) de operação. Para aderência dos microrganismos, empregaram-se como materiais suportes a argila expandida no reator para produção de hidrogênio e as conchas de sururu no reator de produção de metano. Verificou-se a geração de hidrogênio e metano no sistema de duas fases. Foram obtidos maiores rendimento e porcentagem no biogás de hidrogênio no TDH de 2 h, correspondendo aos valores de 2,45 mol H2/mol glicose e 33,82%. Já a maior produção de hidrogênio ocorreu no TDH de 1 h, que foi de 0,57 L/h/L. Para a produção, o rendimento e a porcentagem no biogás de metano, foram observados maiores valores no TDH de 24 h. Tais valores corresponderam, respectivamente, a 1,56 L/h/L, 0,09 L CH4/g DQO e 38,60%. Durante a operação dos reatores, foram observadas, em todas as fases, as presenças de ácido acético, ácido butírico, ácido propiônico, ácido capróico e etanol. Em comparação a outros sistemas de digestão anaeróbia, o sistema de duas fases usado no presente trabalho apresentou parâmetros de desempenho satisfatórios.

Made available in DSpace on 2016-06-02T19:55:33Z (GMT). No. of bitstreams: 1 4623.pdf: 1933289 bytes, checksum: 2fe0862970018a5264c75880e4d507f8 (MD5) Previous issue date: 2012-03-09 / Universidade Federal de Sao Carlos / Hydrogen and ethanol production using microorganisms is a promising area of technological development from a wide variety of renewable and alternative to this production is the use of anaerobic fluidized bed reactor (AFBR). One of the factors that most influence the performance of the AFBR is the material support, which must provide abrasion resistance, porous surface conducive to colonization by microorganisms, easy to achieve fluidization and ability to promote mass transfer between the medium and biofilm. Thus, the objective of this study was to evaluate the influence of different support materials (polystyrene - R1, grounded tire - R2 and polyethylene terephthalate (PET) - R3) on producing hydrogen and ethanol using three anaerobic fluidized bed reactors. Each reactor had a total volume of 4192 cm3 and was fed with media containing glucose as the carbon source (4000 mg L-1) with an influent pH around 5.0 and an effluent pH of about 3.5, a hydraulic retention time (HRT) of 8 1 h at a temperature of 23 2 ºC, with thermal treatment of the inoculum. For hydrogen production, the best performance was achieved with R2 (2.11 mol H2 mol-1 glucose), providing the highest H2 content in biogas (60%). In all reactors, the predominant soluble metabolites were acetic acid, butyric acid, lactic acid and ethanol, with small amounts of propionic acid. The reactor R2 produced more acetic and butyric acid (434.74 and 1013.61 mg L-1, respectively). However, reactor R3 showed a better performance for ethanol production (1941.78 mg L-1). / A produção de hidrogênio e etanol usando microrganismos é uma promissora área de desenvolvimento tecnológico a partir de uma ampla variedade de fontes renováveis e uma das alternativas para esta produção é a utilização do reator anaeróbio de leito fluidizado (RALF). Desta maneira, o objetivo deste trabalho foi avaliar a influência de diferentes materiais suporte (poliestireno - R1, pneu inservível triturado - R2 e PET - R3) visando à produção de hidrogênio e etanol utilizando três reatores anaeróbios de leito fluidizado. Cada reator possuía um volume total de 4192 cm3, alimentado com meio contendo glicose como fonte de carbono (4000 mg.L-1), com tempo de detenção hidráulica (TDH) entre 8 e 1 h a uma temperatura entre 20 e 25ºC, com tratamento térmico do inóculo, utilizando culturas mistas. Para produção de hidrogênio, o melhor desempenho foi do R2, apresentando melhor rendimento de H2 (2,11 mol-H2.mol-1-glicose) e melhor conteúdo de H2 no biogás (60%). Os metabólitos solúveis predominantes em todos os reatores foram ácidos acético e butírico e etanol, havendo uma pequena produção de ácido propiônico, sendo o R2 o que mais produziu ácidos acético e butírico (434,74 e 1013,61 mg/L, respectivamente). Entretanto, o R3 apresentou um melhor desempenho para produção de etanol (2,43 mol-EtOH.mol-1-glicose). Assim, pode-se afirmar que foi possível produzir simultaneamente hidrogênio e etanol como biocombustíveis.

Made available in DSpace on 2016-06-02T19:56:35Z (GMT). No. of bitstreams: 1 2404.pdf: 4034212 bytes, checksum: 2913adf06c11c92402ccb17ed7a97fa8 (MD5) Previous issue date: 2009-02-27 / Universidade Federal de Sao Carlos / Hydrogen is a clean and renewable source of energy and it is considered the "fuel of the future", because it produces only water during combustion and when it is used as fuel and hydrogen has a high energy yield of 122 kJ/g, which is 2.75 times greater than hydrocarbon fuels. The hydrogen production using microorganisms is a promising area of technological development from a wide variety of renewable and a alternative for this production is to use the anaerobic fluidized bed reactor (AFBR), a promising reactor for hydrogen production. One of the factors that most influence the performance of AFBR is the support material, which should provide resistance to abrasion, porous surface conducive to colonization by microorganisms, easy fluidization to reach and ability to facilitate the transfer of mass between the middle and biofilm. Thus, the objective of this study was to evaluate the influence of different support materials (polystyrene - R1, ground tire - R2 and PET - R3) for the hydrogen production, using three AFBR. Each reactor had a total volume of 4192 cm3, which was used as carbon source 4000 mg.L-1 of glucose, with pH influent around 7.0 and pH effluent of around 5.5, with hydraulic retention time (HRT) between 8 and 0.5 h, with temperature of 30 o C } 1, with heat treatment of the inoculum. The best performance was R2, giving better hydrogen yield production (HY) (2.15 mol-H2.mol-1-glucose), best H2 content in the biogas (52.97%) and showed a higher glucose conversion (90%). However, the R3 was better in the hydrogen production rate (HPR), 1.07 lh-1.L-1, a secondary parameter in the analysis of performance of the reactors. In all reactors, the production volume of hydrogen and H2 content in biogas increased with the reduction of the TDH, 8 pm to 1 HEO yield of hydrogen production increased with the reduction of the TDH, 8 h for 2 h. The major soluble metabolites during H2 fermentation were acetic acid (HAc), butyric acid (HBu), lactic acid (HLa) and ethanol (EtOH), and a small production of propionic acid and R2 was the reactor that more produced HAc and HBu (42.0% e 36.5%, respectively) . The better performance of R2 can be explained by the roughness of ground tire is larger than the other materials used, accumulating a large quantity of attached biomass, and a greater quantity of bacteria hydrogen producing. There was a predominance of bacilli like Clostridium sp. in the biofilm of all support materials. / O hidrogenio e uma fonte de energia limpa e renovavel e e considerado o combustivel do futuro , pois gera somente agua durante sua combustao e apresenta calor de combustao de 122 kJ.g-1, o que representa 2,75 vezes mais conteudo de energia do que qualquer hidrocarboneto. A producao de hidrogenio usando microrganismos e uma promissora area de desenvolvimento tecnologico a partir de uma ampla variedade de fontes renovaveis e uma das alternativas para esta producao e a utilizacao do reator anaerobio de leito fluidizado (RALF). Um dos fatores que mais influenciam o desempenho do RALF e o material suporte, que deve apresentar resistencia a abrasao, superficie porosa favoravel a colonizacao de microrganismos, facilidade para alcancar a fluidizacao e capacidade de favorecer a transferencia de massa entre o meio e o biofilme. Desta maneira, o objetivo deste trabalho foi avaliar a influencia de diferentes materiais suporte (poliestireno - R1, pneu inservivel triturado - R2 e PET - R3) na producao de hidrogenio utilizando tres reatores anaerobios de leito fluidizado. Cada reator possuia um volume total de 4192 cm3, alimentado com meio contendo glicose como fonte de carbono (4000 mg.L-1), com pH afluente em torno de 7,0 e efluente em torno de 5,5, com tempo de detencao hidraulica (TDH) entre 8 e 0,5 h a uma temperatura de 30oC } 1oC, com tratamento termico do inoculo. O melhor desempenho foi do R2, apresentando melhor rendimento de H2 (2,15 mol-H2.mol-1-glicose), melhor conteudo de H2 no biogas (52,97%) e maior conversao de glicose (90%). Entretanto, o R3 foi melhor na producao volumetrica de H2, 1,07 L.h-1.L-1, um parametro secundario na analise de desempenho dos reatores. Em todos os reatores, a producao volumetrica de hidrogenio e o conteudo de H2 no biogas aumentaram com a reducao do TDH de 8 h para 1 h e o rendimento de producao de hidrogenio aumentou com a reducao do TDH de 8 h para 2 h. Os metabolitos soluveis predominantes em todos os reatores foram acidos acetico, butirico, latico e etanol, havendo uma pequena producao de acido propionico, sendo o R2 o que mais produziu acidos acetico e butirico (42,0% e 36,5%, respectivamente). O melhor desempenho do R2 pode ser explicado pela rugosidade do pneu triturado ser maior do que a dos demais materiais empregados, acumulando uma maior quantidade de biomassa aderida e uma maior quantidade de bacterias acidogenicas produtoras de hidrogenio. Houve predominancia de bacilos semelhantes a Clostridium sp. no biofilme de todos os materiais suporte.

A digestão anaeróbia tem se apresentado como um processo de grande interesse sob a ótica da potencial produção de energia renovável (H2 e CH4), considerando-se a ampla variedade de compostos orgânicos que podem ser utilizados. Neste estudo desejou-se avançar na compreensão do sistema de reatores anaeróbios de duas fases (acidogênico seguido de metanogênico) operados em condições termofílicas (55°C), alimentados com melaço da cana-de-açúcar, subproduto da indústria sucroalcooleira. Os experimentos foram conduzidos em reatores anaeróbios de leito fixo estruturado com fluxo ascendente e o melaço foi diluído com água de abastecimento, para adequação da concentração aos processos de tratamento de águas residuárias. Na 1ª Etapa dois reatores acidogênicos foram operados em paralelo para avaliar diferentes formas de inoculação e meios suportes, a fim de manter a produção continua e estável de hidrogênio. Para isso foram aplicadas diferentes cargas orgânicas (2,5, 5 e 10 gDQO.L-1) que resultam em COV de 30, 60 e 120 g.DQO.Lreator1.dia-1, com TDH fixo de 2 horas. A expressão do gene hidrogenase foi detectado em ambos os reatores, mas em maior proporção no reator inoculado com lodo de reator UASB e usando como material suporte a espuma de poliuretano. Sequencialmente a este reator, foi acoplado um reator metanogênico, alimentado com efluente do reator acidogênico, estabilizado nas condições apresentadas, e operado com COV crescentes de 1, 2, 5, 7, 14, 17 e 26,5 gDQO.Lreator-1.dia-1 e consequente diminuição do TDH de 240, 96, 48, 32, 24, 16 e 12 horas. O reator acidogênico na 2ª etapa foi operado por 417 dias consecutivos e COV de 120 g.DQO.Lreator1.dia-1, produzindo hidrogênio continuamente, alcançado valores de produção bruta de H2 de 7,60 LH2.dia-1. O reator metanogênico foi operado por 251 dias consecutivos, produzindo metano e alcançado valores de produção bruta de CH4 de 5,90 LCH4.dia-1. A eficiência de remoção de DQO do sistema de reatores foi de aproximadamente 90%, com contribuição aproximadamente de 10% para o reator acidogênico e contribuição aproximadamente de 80% para o reator metanogênico. O reator acidogênico alcançou rendimento de produção de hidrogênio por kg de melaço aplicado de 392 LH2.kgmelaço-1 e o reator metanogênico de 387 LCH4.kgmelaço-1. Para finalidade de comparações e aplicabilidade, o ganho energético global do sistema de reatores de duas fases foi de aproximadamente 5,7 kWh.kgmelaço-1 (1,4 kWh.kgmelaço-1 para o reator acidogênico e 4,3 kWh.kgmelaço-1 para o reator metanogênico). A produção continua de H2 obtida neste estudo está relacionada à associação das vias dos ácidos produtores de hidrogênio já consolidados pela literatura pertinente (acético e butírico) e pela produção de hidrogênio pela rota do ácido lático, devido a associação entre as comunidades de microrganismos estabelecidas no reator. O sequenciamento massivo MiSeq mostrou a seleção de diversos gêneros de microrganismos com redundância funcional e pertencentes principalmente aos Filos Firmicutes, Proteobacteria e Thermotogae, tais como Clostridium sensu stricto, Thermohydrogenium, Thermoanaerobacterium e Cellulosibacter (Firmicutes); Pseudomonas, Enterobacter, Shewanella e Petrobacter (Proteobacteria) e Fervidobacterium (Thermotogae). Microrganismos produtores de ácido lático também foram selecionados tais como: Lactobacillus, Leuconostoc, Sporolactobacillus e Trichococcus. Dos pontos de vista científico e tecnológico este estudo deu mais um passo para a compreensão dos bioprocessos envolvidos nos sistemas anaeróbios em dois estágios produzindo H2 e CH4 continuamente por longo período de tempo. / Anaerobic digestion has shown as an interesting process for renewable energy production (H2 and CH4), for a wide variety of organic compounds (carbon source). This study aimed to advance the understanding of a two-stage process anaerobic system (acidogenic bioreactor followed by methanogenic bioreactor) under thermophilic condition (55°C) fed with molasses, a sugarcane industry by-product. The experiments were conducted at up-flow structured bed reactors and sugarcane molasses was diluted with tap water, to adjust the concentration to the wastewater treatment. At first stage two acidogenic reactors were operated in parallel to evaluate different source of inocula and support bed, to obtain continuous and stable hydrogen production. It was applied 2.5, 5 and 10 gCOD.L-1 resulting in OLR of 30, 60 and 120 g.COD.Lreactor-1.day-1, with HRT fixed at 2 hours of hydrogenase gene was detected in both reactors but with higher number of copies of the gene in the reactor that showed higher hydrogen production: the reactor sed with sludge of UASB reactor and using polyurethane foam as support material. To this reactor was coupled a methanogenic reactor fed with effluent from acidogenic reactor and operated with increasing OLR (1, 2, 5, 7, 14, 17 e 26,5 gCOD.Lreactor-1.day-1) decreasing the HRT (240, 96, 48, 32, 24, 16 and 12 hours). The acidogenic reactor was operated during 471 days with OLR of 120 g.COD.Lreactor-1.day-1, with HRT fixed at 2 hours, with continuous hydrogen production with a gross production of 7.60 LH2.day-1. The methanogenic reactor was operated for 251 days, with continuous methane production of up to 5.90LCH4.day-1. The COD removal efficiency using the two-stage system was approximately 90% , with 10% contribution by the acidogenic reactor and 80% contribution by the methanogenic reactor. The acidogenic reactor achieved hydrogen yield per kg of applied molasses equal to 392 LH2.kgmolases-1. The methanogenic reactor achieved methane yield per kg of applied molasses equal to 387 LCH4.kgmolasses-1. For comparison and applicability purposes, the overall energy yield using the two stage reactor system was approximately 5.7 kWh.kgmolasses-1 (Acidogenic reactor 1.4 kWh.kgmolasses-1 and Methanogenic reactor 4.3 kWh.kgmolasses-1). The continuous production of H2 obtained in this study is related to the association of the hydrogen producer acids pathway established by the relevant literature (acetic and butyric) and the hydrogen production by the lactic acid pathway due to the microorganisms association established in the reactor. Metagenomic analysis by MiSeq Plataform revealed that hydrogen production was due the selection of microorganisms with functional redundancy mainly of Phyla Firmicutes, Proteobacteria and Thermotogae, such as Clostridium sensu stricto, Thermohydrogenium, Thermoanaerobacterium, Cellulosibacter (Firmicutes); Pseudomonas, Enterobacter, Shewanella and Petrobacter (Proteobacteria) and Fervidobacterium (Thermotogae). Genera of acid latic producers, such as Lactobacillus, Leuconostoc, Sporolactobacillus and Trichococcus, were also selected. From the scientific and technological point of view this study has taken another step towards the understanding of bioprocesses involving two stage anaerobic systems for a long term continuous production of H2 and CH4.

Abstract The energy consumption around the globe is on the rise due to the exponential population growth and urbanization. There is a need for alternative and non-conventional energy sources, which are CO2-neutral, and a need to produce less or no environmental pollutants and to have high energy efficiency. One of the alternative approaches is hydrogen economy with the fuel cell (FC) technology which is forecasted to lead to a sustainable society. Hydrogen (H2) is recognized as a potential fuel and clean energy carrier being at the same time a carbon-free element. Moreover, H2 is utilized in many processes in chemical, food, metallurgical, and pharmaceutical industry and it is also a valuable chemical in many reactions (e.g. refineries). Non-renewable resources have been the major feedstock for H2 production for many years. At present, ~50% of H2 is produced via catalytic steam reforming of natural gas followed by various down-stream purification steps to produce ~99.99% H2, the process being highly energy intensive. Henceforth, bio-fuels like biomass derived alcohols (e.g. bio-ethanol and bio-glycerol), can be viable raw materials for the H2 production. In a membrane based reactor, the reaction and selective separation of H2 occur simultaneously in one unit, thus improving the overall reactor efficiency. The main motivation of this work is to produce H2 more efficiently and in an environmentally friendly way from bio-alcohols with a high H2 selectivity, purity and yield. In this thesis, the work was divided into two research areas, the first being the catalytic studies using metal decorated carbon nanotube (CNT) based catalysts in steam reforming of ethanol (SRE) at low temperatures (<450 °C). The second part was the study of steam reforming (SR) and the water-gas-shift (WGS) reactions in a membrane reactor (MR) using dense and composite Pd-based membranes to produce high purity H2. CNTs were found to be promising support materials for the low temperature reforming compared to conventional catalyst supports, e.g. Al2O3. The metal/metal oxide decorated CNTs presented active particles with narrow size distribution and small size (~2–5 nm). The ZnO promoted Ni/CNT based catalysts showed the highest H2 selectivity of ~76% with very low CO selectivity <1%. Ethanol was shown to be a more suitable and viable source for H2 than glycerol. The dense Pd-Ag membrane had higher selectivity but a lower permeating flux than the composite membrane. The MR performance is also dependent on the active catalyst materials and thus, both the catalyst and membrane play an important role. Overall, the membrane–assisted reformer outperforms the conventional reformer and it is a potential technology in pure H2 production. The high purity of H2 gas with a CO-free reformate for fuel cell applications can be gained using the MR system. / Tiivistelmä Maailman energiankulutus on kasvussa räjähdysmäisen väestönkasvun ja voimakkaan kaupungistumisen myötä. Tällä hetkellä energian tuottamisen aiheuttamat ympäristöongelmat ja taloudellinen epävarmuus ovat seikkoja, joiden ratkaisemiseksi tarvitaan vaihtoehtoisia ja ei-perinteisiä energialähteitä, joilla on korkea energiasisältö ja jotka tuottavat vähän hiilidioksidipäästöjä. Eräs vaihtoehtoisista lähestymistavoista on vetytalous yhdistettynä polttokennotekniikkaan, minkä on esitetty helpottavan siirtymistä kestävään yhteiskuntaan. Vety on puhdas ja hiilivapaa polttoaine ja energian kantaja. Lisäksi vetyä käytetään monissa prosesseissa kemian-, elintarvike-, metalli- ja lääketeollisuudessa ja se on arvokas kemikaali monissa prosesseissa (mm. öljynjalostamoissa). Uusiutumattomat luonnonvarat ovat olleet tähän saakka merkittävin vedyn tuotannon raaka-aine. Tällä hetkellä noin 50 % vedystä tuotetaan maakaasun katalyyttisellä höyryreformoinilla. Puhtaan (yli 99,99 %) vedyn tuotanto vaatii kuitenkin useita puhdistusvaiheita, jotka ovat erittäin energiaintensiivisiä. Integroimalla reaktio- ja puhdistusvaihe samaan yksikköön (membraanireaktori) saavutetaan huomattavia kustannussäästöjä. Biopolttoaineet, kuten biomassapohjaiset alkoholit (bioetanoli ja bioglyseroli), ovat vaihtoehtoisia lähtöaineita vedyn valmistuksessa. Tämän työn tavoitteena on tuottaa vetyä bioalkoholeista tehokkaasti (korkea selektiivisyys ja saanto) ja ympäristöystävällisesti. Tutkimus on jaettu kahteen osaan, joista ensimmäisessä tutkittiin etanolin katalyyttistä höyryreformointia matalissa lämpötiloissa (<450 °C) hyödyntämällä metallipinnoitettuja hiilinanoputkia. Työn toisessa osassa höyryreformointia ja vesikaasun siirtoreaktioa tutkittiin membraanireaktorissa käyttämällä vedyn tuotantoon tiheitä palladiumpohjaisia kalvoja sekä huokoisia palladiumkomposiittikalvoja. Hiilinanoputket (CNT) havaittiin lupaaviksi katalyyttien tukimateriaaleiksi verrattuna tavanomaisesti valmistettuihin tukiaineisiin, kuten Al2O3. CNT-tukiaineelle pinnoitetuilla aktiivisilla aineilla (metalli-/metallioksidit) todettiin olevan pieni partikkelikoko (~2–5 nm) ja kapea partikkelikokojakauma. Sinkkioksidin (ZnO) lisäyksellä Ni/CNT-katalyytteihin saavutettiin korkea vetyselektiivisyys (~76 %) ja erittäin alhainen hiilimoksidiselektiivisyys (<1 %). Etanolin todettiin olevan parempi vedyn raaka-aine kuin glyserolin. Tiheillä Pd-Ag-kalvoilla havaittiin olevan vedyn suhteen korkeampi selektiivisyys mutta matalampi vuo verrattuna palladiumkomposiittikalvoihin. Membraanireaktorin suorituskyky oli riippuvainen myös katalyytin aktiivisuudesta, joten sekä kalvolla että katalyyttimateriaalilla oli merkittävä rooli kyseisessä reaktorirakenteessa. Yhteenvetona voidaan todeta, että membraanierotukseen perustuva reformointiyksikkö on huomattavasti perinteistä reformeriyksikköä suorituskykyisempi mahdollistaen tehokkaan teknologian puhtaan vedyn tuottamiseksi. Membraanitekniikalla tuotettua puhdasta vetyä voidaan hyödyntää mm. polttokennojen polttoaineena.