In the last couple of years there has been a great need for finding alternative, cleaner burning fuel sources. This search has led to the development of various hydrogen technologies. The reason for this is that when burnt, hydrogen gas only forms water and oxygen as products. One of the methods used in the production of hydrogen gas is that of the electrolysis of sulphur dioxide which is facilitated by a sulphur dioxide depolarized electrolyzer. The electrolysis of sulphur dioxide has the advantage of requiring lower cell voltages in the electrolysis process when compared to the electrolysis of water. This type of electrolyzer unfortunately suffers from low hydrogen gas production volumes. It was thought that by linearly increasing the reactions active area of the electrolyzer, the production volumes can be increased. A linearly upscaled 100cm2 cell was designed by using computer aided design software, such as SolidWorks, Cambridge Engineering Selector, EES and ANSYS. The cell was then constructed and tested to determine the effects of linearly upscaling. The results of the 100cm2 cell were compared to the results of a similar 25cm2 cell and results obtained from the literature. The 100cm2 cell exhibited very poor performance when compared to the other cells. The 100cm2 cell showed lower hydrogen production volumes at higher energy inputs than the 25cm2 cell and an 86cm2 stack assembly. It was concluded that creating stack assemblies with cells with smaller active areas would be much more efficient than linearly upscaling the active area of the cells. / Thesis (M.Ing. (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2012.

La production biologique d'hydrogène (H2) représente une technologie possible pour la production à grande échelle durable de H2 nécessaire pour l'économie future de l'hydrogène. Cependant, l'obstacle majeur à l'élaboration d'un processus pratique a été la faiblesse des rendements qui sont obtenus, généralement autour de 25%, bien en sous des rendements pouvant être atteints pour la production de biocarburants à partir d'autres processus. L'objectif de cette thèse était de tenter d'améliorer la production d'H2 par la manipulation physiologique et le génie métabolique. Une hypothèse qui a été étudiée était que la production d'H2 pourrait être améliorée et rendue plus économique en utilisant un procédé de fermentation microaérobie sombre car cela pourrait fournir la puissance supplémentaire nécessaire pour une conversion plus complète du substrat et donc une production plus grande d'H2 sans l'aide de l'énergie lumineuse. Les concentrations optimales d’O2 pour la production de H2 microaérobie ont été examinées ainsi que l'impact des sources de carbone et d'azote sur le processus. La recherche présentée ici a démontré la capacité de Rhodobacter capsulatus JP91 hup- (un mutant déficient d’absorption-hydrogénase) de produire de l'H2 sous condition microaérobie sombre avec une limitation dans des quantités d’O2 et d'azote fixé. D'autres travaux devraient être entrepris pour augmenter les rendements d'H2 en utilisant cette technologie. De plus, un processus de photofermentation a été créé pour améliorer le rendement d’H2 à partir du glucose à l'aide de R. capsulatus JP91 hup- soit en mode non renouvelé (batch) et / ou en conditions de culture en continu. Certains défis techniques ont été surmontés en mettant en place des conditions adéquates de fonctionnement pour un rendement accru d'H2. Un rendement maximal de 3,3 mols de H2/ mol de glucose a été trouvé pour les cultures en batch tandis que pour les cultures en continu, il était de 10,3 mols H2/ mol de glucose, beaucoup plus élevé que celui rapporté antérieurement et proche de la valeur maximale théorique de 12 mols H2/ mol de glucose. Dans les cultures en batch l'efficacité maximale de conversion d’énergie lumineuse était de 0,7% alors qu'elle était de 1,34% dans les cultures en continu avec un rendement de conversion maximum de la valeur de chauffage du glucose de 91,14%. Diverses autres approches pour l'augmentation des rendements des processus de photofermentation sont proposées. Les résultats globaux indiquent qu'un processus photofermentatif efficace de production d'H2 à partir du glucose en une seule étape avec des cultures en continu dans des photobioréacteurs pourrait être développé ce qui serait un processus beaucoup plus prometteur que les processus en deux étapes ou avec les co-cultures étudiés antérieurément. En outre, l'expression hétérologue d’hydrogenase a été utilisée comme une stratégie d'ingénierie métabolique afin d'améliorer la production d'H2 par fermentation. La capacité d'exprimer une hydrogénase d'une espèce avec des gènes de maturation d'une autre espèce a été examinée. Une stratégie a démontré que la protéine HydA orpheline de R. rubrum est fonctionnelle et active lorsque co-exprimée chez Escherichia coli avec HydE, HydF et HydG provenant d'organisme différent. La co-expression des gènes [FeFe]-hydrogénase structurels et de maturation dans des micro-organismes qui n'ont pas une [FeFe]-hydrogénase indigène peut entraîner le succès dans l'assemblage et la biosynthèse d'hydrogénase active. Toutefois, d'autres facteurs peuvent être nécessaires pour obtenir des rendements considérablement augmentés en protéines ainsi que l'activité spécifique des hydrogénases recombinantes. Une autre stratégie a consisté à surexprimer une [FeFe]-hydrogénase très active dans une souche hôte de E. coli. L'expression d'une hydrogénase qui peut interagir directement avec le NADPH est souhaitable car cela, plutôt que de la ferrédoxine réduite, est naturellement produit par le métabolisme. Toutefois, la maturation de ce type d'hydrogénase chez E. coli n'a pas été rapportée auparavant. L'opéron hnd (hndA, B, C, D) de Desulfovibrio fructosovorans code pour une [FeFe]-hydrogénase NADP-dépendante, a été exprimé dans différentes souches d’E. coli avec les gènes de maturation hydE, hydF et hydG de Clostridium acetobutylicum. L'activité de l'hydrogénase a été détectée in vitro, donc une NADP-dépendante [FeFe]-hydrogénase multimérique active a été exprimée avec succès chez E. coli pour la première fois. Les recherches futures pourraient conduire à l'expression de cette enzyme chez les souches de E. coli qui produisent plus de NADPH, ouvrant la voie à une augmentation des rendements d'hydrogène via la voie des pentoses phosphates. / Biological hydrogen (H2) production represents a possible technology for the large scale sustainable production of H2 needed for a future hydrogen economy. However, the major obstacle to developing a practical process has been the low yields that are obtained, typically around 25%, well below those achievable for the production of other biofuels from the same feedstock. The goal of this thesis was to improve H2 production through physiological manipulation and metabolic engineering. One investigated hypothesis was that H2 production could be improved and made more economical by using a microaerobic dark fermentation process since this could provide the extra reducing power required for driving substrate conversion to completion and hence more H2 production might be obtained without using light energy. The optimal O2 concentrations for microaerobic H2 production were examined as well as the impact of carbon and nitrogen sources on the process. The research reported here proved the capability of Rhodobacter capsulatus JP91 hup- (an uptake-hydrogenase deficient mutant) to produce H2 under microaerobic dark conditions with limiting amounts of O2 and fixed nitrogen. Further work should be undertaken to increase H2 yields using this technology. In addition, a photofermentation process was established to improve H2 yield from glucose using R. capsulatus JP91 hup- strain either in batch and/or continuous culture conditions. Some technical challenges in establishing the proper operational conditions for increased H2 yield were overcome. A maximum yield of 3.3 mols of H2/ mol of glucose was found for batch cultures whereas in continous cultures it was 10.3 mols H2/ mol glucose, much higher than previously reported and close to the theoretical maximum value of 12 mols H2/ mol glucose. In batch cultures the maximum light conversion efficiency was 0.7% whereas it was 1.34% in continuous cultures with a maximum conversion efficiency of the heating value of glucose of 91.14%. Various approaches to further increasing yields in photofermentation processes are proposed. The overall results suggest that an efficient single stage photofermentative H2 production process from glucose using continuous cultures in photobioreactors could be developed which would be a much more promising alternative process to the previously studied two stage photofermentation or co-culture approaches. Furthermore, the heterologous expression of hydrogenases was used as a metabolic engineering strategy to improve fermentative H2 production. The capability of expressing a hydrogenase from one species with the maturation genes from another was examined. One strategy demonstrated that the orphan hydA of R. rubrum is functional and active when co-expressed in E. coli with hydE, hydF and hydG from different organisms. Co-expression of the [FeFe]-hydrogenase structural and maturation genes in microorganisms that lack a native [FeFe]-hydrogenase can successfully result in the assembly and biosynthesis of active hydrogenases. However, other factors may be required for significantly increased protein yields and hence the specific activity of the recombinant hydrogenases. Another strategy was to overexpress one of the highly active [FeFe]-hydrogenases in a suitable E. coli host strain. Expression of a hydrogenase that can directly interact with NADPH is desirable as this, rather than reduced ferredoxin, is naturally produced by its metabolism. However, the successful maturation of this type of hydrogenase in E. coli had not been previously reported. The Desulfovibrio fructosovorans hnd operon (hndA, B, C, and D genes), encoding a NADP-dependent [FeFe]-hydrogenase, was expressed in various E. coli strains with the maturation genes hydE, hydF and hydG of Clostridium acetobutylicum. Hydrogenase activities were detected in vitro, thus a multi-subunit NADP-dependent [FeFe]-active hydrogenase was successfully expressed and matured in E. coli for the first time. Future research could lead to the expression of this hydrogenase in E. coli host strains that overproduce NADPH, setting the stage for increased hydrogen yields via the pentose phosphate pathway.

Conversion of natural gas and other light hydrocarbons via steam reforming is currently the major process for hydrogen production. However, conventional hydrogen production technologies are not cost effective and therefore, cost is the biggest impediment to use hydrogen in fuel cell applications. In order to optimize and overcome cost problems in hydrogen production, sorption and membrane enhanced reaction processes are the two novel technologies for in situ operation of reforming and removal of carbon dioxide. Adsorption of carbon dioxide onto activated hydrotalcite and activated soda, obtained from either trona or NaHCO3, had been studied using a stainless steel packed bed tubular reactor as a function of temperature. Adsorption of CO2 in the presence and absence of steam onto activated hydrotalcite was conducted in the temperature range of 400-527 oC, whereas sorption studies with activated soda were performed for 80 to 152 oC in the presence of steam. Also, two-parameter deactivation model was developed to justify the experimental data and predictions of the breakthrough curves by deactivation model indicated a good agreement with the experimental results. In order to obtain physical properties of the sorbents, untreated and calcined sorbents were characterized by using TGA, B.E.T (N2 adsorption), and Hg porosimetry techniques. When hydrotalcite was used as the sorbent, total adsorption capacity of the material reduced from 1.18 mol/kg to 0.66 mol/kg as the temperature was increased from 400 oC to 527 oC. On the other hand, activated soda exhibited a total adsorption capacity 1.15 to 0.68 mol/kg for a temperature change from 80 to 152 oC. For high temperature removal of CO2, hydrotalcite and its promoted forms (using K2CO3 or Na2CO3) are pretty good sorbents to be used in single step hydrogen production processes, such as SERP. On the other hand, activated soda could also be used for CO2 abatement of the effluent gas from the reformer only when the temperature is lowered enough to obtain efficient adsorption capacity within the multi-bed adsorbers.

Στην παρούσα διατριβή μελετήθηκε η δυνατότητα αξιοποίησης της γλυκερόλης η οποία αποτελεί ένα σημαντικό παραπροϊόν της βιομηχανίας του βιοντήζελ. Συνήθως αντιστοιχεί στο 10% της παραγόμενης ποσότητας του βιοντήζελ. Αυτό το γεγονός συντέλεσε στην υπερβολική αύξηση της παραγωγής της γλυκερόλης σε παγκόσμιο επίπεδο. Η περίσσεια της γλυκερόλης δε μπορεί να απορροφηθεί από τους συνηθισμένους βιομηχανικούς κλάδους που τη χρησιμοποιούν. Επομένως θα πρέπει να βρεθεί τρόπος αξιοποίησης αυτού του συσσωρευμένου παραπροϊόντος. Η κλασική μέθοδος επεξεργασίας αφορά τη χημική οδό μέσω της οποίας η γλυκερόλη μπορεί να μετατραπεί σε άλλα χημικά μόρια. Από την άλλη πλευρά βιοχημικές διεργασίες όπως η αναερόβια χώνευση, η ζύμωση αλλά και η μικροβιακή κυψελίδα καυσίμου μπορούν να μετατρέψουν τη γλυκερόλη σε μεθάνιο, υδρογόνο και ηλεκτρικό ρεύμα αντίστοιχα. Οι διεργασίες αυτές, οι οποίες αποτέλεσαν και το αντικείμενο έρευνας της διατριβής, είναι λιγότερο δαπανηρές από τις χημικές και επιβαρύνουν λιγότερο το περιβάλλον. Η διεργασία της αναερόβιας χώνευσης διεξήχθη σε συμβατικό αντιδραστήρα τύπου CSTR και σε ταχύρυθμο τύπου PABR. Στα πειράματα μελετήθηκε η επίδραση της συγκέντρωσης της γλυκερόλης στο ρυθμό παραγωγής του μεθανίου. Από τα αποτελέσματα που λήφθησαν φάνηκε ότι ο CSTR δεν άντεχε οργανική φόρτιση πέραν των 0.25 g COD/L/d, ενώ από την άλλη πλευρά ο PABR λειτούργησε σε υπερ 10-πλάσια φόρτιση της τάξης των 3 g COD/L/d με παραγωγή μεθανίου 0.982 ± 0.089 L/L/d. Με το πέρας της πειραματικής διαδικασίας ακολούθησε μοντελοποίηση της διεργασίας, αρχικά για την περίπτωση του CSTR και κατόπιν χρησιμοποιήθηκε το ίδιο μοντέλο με τροποποίηση για την περίπτωση του PABR. Η ζυμωτική παραγωγή του υδρογόνου διεξήχθη επιτυχώς σε αντιδραστήρες διαλείποντος έργου. Μελετήθηκε η επίδραση της αρχικής συγκέντρωσης της γλυκερόλης και η επίδραση του αρχικού pH στην παραγωγή του υδρογόνου. Βρέθηκε ότι η μέγιστη παραγωγή υδρογόνου, 27.3 mL H2/ g COD γλυκερόλης, προήθλε όταν η αρχική συγκέντρωση είχε τεθεί στα 8.3 g COD/L. Η ζυμωτική παραγωγή υδρογόνου φάνηκε να ευνοείται σε pH γύρω από το 6.5. Εν συνεχεία, εξετάστηκε η ζυμωτική παραγωγή υδρογόνου σε συνεχή αντιδραστήρα. Η παραγωγή του υδρογόνου ήταν υπερβολικά ασταθής, γεγονός που πιθανότατα να οφείλεται στην απομάκρυνση της υδρογονοπαραγωγού βιομάζας από τον αντιδραστήρα σε συνδυασμό με την παρουσία υδρογονοκαταναλωτών μικροοργανισμών. Για την παραγωγή ηλεκτρικού ρεύματος από γλυκερόλη χρησιμοποιήθηκε μικροβιακή κυψελίδα καυσίμου διάταξης Η-type σε συνθήκες διαλείποντος έργου. Μελετήθηκε η επίδραση της αρχικής συγκέντρωσης της γλυκερόλης στην παραγωγή ηλεκτρικού ρεύματος. Παρατηρήθηκε ότι η συγκέντρωση των 3.2 g COD/L απέφερε τη μέγιστη απόδοση Coulomb (CE) 34.09 %. Η περαιτέρω αύξηση της συγκέντρωσης οδήγησε σε μείωση της CE. Αυτό ίσως να οφείλεται σε κινητικό περιορισμό που υπέστησαν οι ηλεκτροχημικά ενεργοί μικροοργανισμοί όταν εκτέθηκαν σε υψηλές συγκεντρώσεις γλυκερόλης. / This study focused on the valorization of glycerol which is an important by-product of the biodiesel industry corresponding to 10 % of the produced biodiesel amount. This fact contributed to the increase of the global production of biodiesel, to a point at which the industries which traditionally consumed glycerol could not absorb. This situation should be overcome through new outlets on glycerol exploitation. Usually, glycerol is treated by chemical processes in order to form new chemical compounds. On the other side, biochemical processes like anaerobic digestion and fermentation or the technology of microbial fuel cells could potentially transform glycerol into methane, hydrogen and electric current respectively. These processes, which are the subject of this Ph.d, are preferable to their chemical counterparts due to the low energy demand and reduced environmental pollution. The anaerobic digestion process was conducted in a conventional CSTR reactor and in a high rate reactor, the PABR. The experiments dealt with the effect of glycerol concentration on the methane production rate. The obtained results showed that the CSTR could not withstand organic loadings above 0.25 g COD/L/d, however PABR operated at organic loading 10 times higher than CSTR such as 3 g COD/L/d and resulted to a methane production rate of 0.982 ± 0.089 L/L/d. A model was developed for both the CSTR and the PABR digesters. Fermentative hydrogen production was conducted successfully in batch reactors. The effect of the initial glycerol concentration and initial pH on hydrogen production was studied. A maximum yield, 27.3 mL H2/ g COD glycerol, was obtained when glycerol concentration was 8.3 g COD/L and the pH 6.5. Moreover, the fermentation of glycerol took place in a CSTR in order to investigate the continuous production of hydrogen. Hydrogen production was unstable, possibly due to the washout of proper biomass from the reactor. For electricity generation from glycerol, an H-type microbial fuel cell was used in batch mode. The effect of the initial glycerol on the electric current was studied. A maximum Coulombic efficiency (CE) 34.09% was obtained at a glycerol concentration of 3.2 g COD/L. A further increase of glycerol drove to a drop of the CE. Probably, this happened since the electrochemical microorganisms were inhibited by the high glycerol concentration.

Afin d’améliorer les performances électrochimiques de cellules d’électrolyse de la vapeur d’eau à haute température (EVHT), de nouveaux matériaux d’électrode à oxygène de typeLn2NiO4+δ (Ln = La, Pr ou Nd), Pr4Ni3O10±δ et La0,6Sr0,4Fe0,8Co0,2O3-δ ont été étudiés. Ces composés ont été sélectionnés pour leurs propriétés de conduction mixte électronique et ionique. Après la caractérisation de leurs propriétés physico-chimiques, les matériaux ont été mis en forme au sein de demi-cellules symétriques, en intercalant une couche d’interface fine à base de cérine entre l’électrode et l’électrolyte de zircone yttriée. Cette architecture contribue à la diminution de la résistance de polarisation de l’électrode (RP <0,1 Ω.cm2 à 800°C) et de la surtension anodique. Un modèle électrochimique a été développé afin de décrire et d’analyser les courbes de polarisation expérimentales.L’électrode présentant les plus faibles surtensions, Pr2NiO4+δ, a été sélectionnée et caractérisée au sein de cellules complètes à cermet support. En fonctionnement EVHT à800°C, une densité de courant élevée a été obtenue, de l’ordre de i = -0,9 A.cm-2 pour une tension de cellule de 1,3V et un taux de conversion d’environ 60%. / In order to improve the electrochemical performances of cells for high temperature steam electrolysis (HTSE), innovative oxygen electrode materials have been studied. The compounds Ln2NiO4+δ (Ln = La, Pr or Nd), Pr4Ni3O10±δ and La0.6Sr0.4Fe0.8Co0.2O3-δ have been selected for their mixed electronic and ionic conductivity. First, their physical and chemical properties have been investigated. Then, the electrodes were shaped on symmetrical half cells,adding a thin ceria-based interlayer between the electrode and the yttria doped zirconia-based electrolyte. These architectured cells lead to low polarization resistances (RP< 0.1 Ω.cm2 at 800°C) as well as reduced anodic over potentials . An electrochemical model has been developed in order to describe and analyze the experimental polarization curves.The electrode with the lower overpotential, i.e. Pr2NiO4+δ, has been selected and characterized into complete cermet-supported cells. Under HTSE operation, at 800°C, a high current density was measured, close to i = -0.9 A.cm-2 for a cell voltage equals to 1.3 V, the conversion rate being about 60%.

Hydrogen has been studying as an alternative energy source to replace fossil fuels. This is justified because, in its combustion is generating primarily water vapor and by its energy content is approximately 2.5 times greater than any fossil fuel. Besides these advantages, hydrogen can be produced from renewable sources, such as various types of industrial and domestic waste rich in carbohydrates. Thus, the purpose of this study was to evaluate the production of hydrogen from a substrate real, the manipueira (wastewater processing cassava), as carbon source in anaerobic fluidized bed reactor (AFBR) operated under a progressive increase in the organic loading rate (OLR). The support material for the adhesion of biomass has been expanded clay (2.8 to 3.35 mm) and the reactor was inoculated with anaerobic sludge thermal pretreatment. The reactor was operated for 164 days and gradually increasing the organic loading rate was obtained by maintaining a constant influent COD (4000 mg. L-1) throughout the operation of the reactor and varying the hydraulic retention time (HRT) of 8 to 1 hour. The production of hydrogen ranged from 0.20 to 2.04 L.h-1.L-1, when the HRT reduced from 8 h to 1 h. The yield had an increase from 0.31 to 1.91 mol H2.mol glucose-1 by reducing the HRT from 8 to 2 h. By lowering the HRT for 1 h, the yield was reduced, reaching a value of 1.20 mol H2.mol glucose-1. The soluble metabolites present during the operation of the reactor were acetic acid, butyric acid, propionic acid and ethanol. The microscopic analysis indicated the presence of bacilli, which are morphologies similar to species of the genus Clostridium sp. and Enterobacter sp., which are known as potential production of hydrogen in fermentation processes. / Conselho Nacional de Desenvolvimento Científico e Tecnológico / O hidrogênio vem sendo estudado como fonte alternativa de energia em substituição aos combustíveis fósseis. Isso porque, na sua combustão há geração principalmente de vapor de água e por seu conteúdo energético ser aproximadamente 2,5 vezes maior do que qualquer combustível fóssil. Além dessas vantagens, o hidrogênio pode ser produzido a partir de fontes renováveis, tais como os diversos tipos de resíduos industriais e domésticos ricos em carboidratos. Dessa forma, o objetivo da pesquisa foi avaliar a produção de hidrogênio a partir de um substrato real, a manipueira (água residuária do processamento da mandioca), como fonte de carbono em reator anaeróbio de leito fluidificado (RALF) operado sob aumento progressivo da taxa de carregamento orgânico (TCO). O material suporte para a aderência da biomassa foi argila expandida com diâmetro entre 2,8 3,35 mm e o reator foi inoculado com lodo anaeróbio pré-tratado termicamente. O reator foi operado por 164 dias e o aumento progressivo da taxa de carregamento orgânico foi realizado mantendo a DQO afluente constante (4000 mg. L-1) durante toda a operação do reator e variando o tempo de detenção hidráulica (TDH) de 8 horas até 1 hora. Foi constatado que a produção volumétrica de hidrogênio aumentou de 0,20 até 2,04 L.h-1.L-1, quando foi reduzido o TDH de 8 h para 1 h. E o rendimento sofreu um incremento de 0,31 até 1,91 mol H2.mol glicose-1, com a redução do TDH de 8 para 2 h. Ao reduzir o TDH para 1 h, o rendimento sofreu uma redução, atingindo o valor de 1,20 mol H2.mol glicose-1. Os metabólitos solúveis presentes durante a operação do reator foram o ácido acético, ácido butírico, ácido propiônico e etanol. As análises microscópicas indicaram a presença de bacilos, os quais são morfologias semelhantes às espécies dos gêneros Clostridium sp. e Enterobacter sp., que são conhecidas como potenciais produtoras de hidrogênio em processos fermentativos.

Made available in DSpace on 2016-06-02T19:55:32Z (GMT). No. of bitstreams: 1 4549.pdf: 10506362 bytes, checksum: 622f533bcc042279d1b10154620ecb35 (MD5) Previous issue date: 2012-06-11 / Financiadora de Estudos e Projetos / Cobalt-based catalysts supported on &#947;-alumina and magnesium aluminate modified with lanthanum and cerium have been applied to various conditions of reforming of ethanol. The initial challenge was to control the rate of carbon accumulation, a major cause of deactivation of catalysts under steam reforming of ethanol. In situ X-ray absorption spectroscopy analyses showed that the rate of carbon accumulation is inversely proportional to the amount of Co2+ species and directly proportional to the amount of Co0 species. X-ray photoelectron spectroscopy analyses showed that, after reducing the catalysts in hydrogen, the oxidized fraction of the particles is mainly on their surface. Both the oxidized and reduced fractions of cobalt crystallites have face-centered cubic structure. The concentration of superficial oxygen under reforming conditions is determined by the curvature of the surface of the particles, the nature of the supports and the presence of promoters such as platinum and copper. The concentration of superficial oxygen is also highly sensitive to reaction conditions such as the composition and amount of oxidizing agents, such as oxygen and water, and reaction temperature. The rate of accumulation of carbon could be controlled with co-feeding oxygen to the reactor, process called oxy-reforming of ethanol, and using ceria as support. However, stability tests showed that catalyst deactivation may also occur by oxidation of metal sites. The ignition of the reforming process takes place in a microregion at the entrance of the catalyst bed where ethanol is fully oxidized, releasing energy and increasing the local temperature. Spatial-resolved X-ray absorption spectroscopy analyses showed that the ratio Co2+/Co0 is much greater than one inside this microregion. The high local temperature and the presence of oxidized species in the entrance of the bed produce the appropriate conditions which lead the Co2+ ions to diffuse into the defect spinel structure of &#947;-alumina, leading to loss of potentially active sites for reforming of ethanol. This phenomenon is unleashed as a wave that propagates from the entrance of the bed downstream to the regions where Co2+ species exist. However, one can prevent the diffusion of Co2+ species to the structure of &#947;- alumina using aluminates as supports. / Catalisadores de cobalto suportados em &#947;-alumina e aluminato de magnésio modificados com lantânio e cério foram aplicados a diferentes condições de reforma do etanol. O desafio inicial foi tentar controlar a taxa de acúmulo de carbono, um dos principais fatores de desativação de catalisadores em condições de reforma a vapor do etanol. Análises de espectroscopia de absorção de raios X in situ comprovaram que a diminuição da taxa de acúmulo de carbono está ligada ao aumento da quantidade de espécies Co2+ em relação à quantidade de espécies Co0 nas partículas de cobalto. Análises de espectroscopia de fotoelétrons excitados por raios X demonstraram que, após redução em hidrogênio, a fração oxidada das partículas encontra-se majoritariamente na superfície das mesmas. Ambas as frações oxidadas e reduzidas das partículas de cobalto apresentam estrutura cúbica de face centrada. A concentração de oxigênio superficial em condições de reforma do etanol é determinada pela curvatura da superfície das partículas, pela natureza dos suportes e pela presença de promotores tais como platina e cobre. A concentração de oxigênio superficial é também fortemente sensível às condições de reação, tais como a composição e quantidade de agentes oxidantes, como a água e o oxigênio, e a temperatura de reação. O acúmulo de carbono pôde ser controlado com a coalimentação de oxigênio ao reator, processo denominado reforma a vapor com coalimentação de oxigênio, e utilizando-se céria como suporte. Entretanto, testes de estabilidade demonstraram que a desativação do catalisador pode também ocorrer por oxidação dos sítios metálicos. A ignição da reforma ocorre em uma microrregião na entrada do leito catalítico onde o etanol é completamente oxidado, liberando energia e aumentando a temperatura local. Análises de espectroscopia de absorção de raios X in situ resolvidas no espaço demonstraram que, nesta microrregião, a razão Co2+/Co0 é muito maior que um. O aumento da temperatura local e a presença de espécies oxidadas na entrada do leito produzem as condições adequadas para que íons Co2+ se difundam na estrutura espinela defeituosa da &#947;- alumina, levando a perdas de sítios potencialmente ativos para a reforma do etanol. Este fenômeno se deflagra como uma onda de desativação que se propaga da entrada do leito em direção às regiões à jusante onde existem espécies Co2+. Por outro lado, pode-se evitar a difusão de espécies Co2+ na estrutura da &#947;-alumina utilizando-se aluminatos como suporte.

Made available in DSpace on 2016-06-02T19:55:39Z (GMT). No. of bitstreams: 1 5956.pdf: 2655473 bytes, checksum: dfaa0329652cfa24fb1dd3934c5b664b (MD5) Previous issue date: 2014-03-28 / Universidade Federal de Sao Carlos / The aim of this study was to evaluate the influence of hydraulic retention time (HRT), the origin of different inoculum (sludge from a UASB reactor for swine wastewater treatment and poultry slaughterhouse), and different carbon source (glucose, cassava processing wastewater and cheese whey) on the stability and efficiency of the anaerobic fluidized bed reactor (AFBR) for producing hydrogen. Twelve identical reactors were used, and in two reactors the mixture of glucose with cheese whey (R1S, R2S) was used as a substrate, six reactors were used with mix cassava processing wastewater and glucose (R1M, R2M, R3M and R4M). It was evaluated use of cheese whey (R3S, R4S, R5s and R6S) and cassava processing wastewater (R5M and R6M). The AFBRs were inoculated with sludge from a UASB reactor used in the treatment of swine wastewater (R1S, R3S, R1M, R3M, R5S, R6S, R5M and R6M) and sludge from a UASB reactor that treated poultry slaughterhouse wastewater (R2S, R4S, R2M, R4M), both heat treated. Variations of HRT (12-1 h) and substrate concentrations were performed (2-15 g .L -1), with temperature control at 30 ° C. The reactors that used cheese whey as substrate showed a greatest potential for hydrogen production, with yields (HY) of 3.2 mmolH2.g-1COD (R6S) and 2.6 mmolH2.g-1COD (R5S) were obtained by applying a HRT of 6 and 14 hours, with a concentration of 3 and 5 g.L-1, respectively. Both substrates showed potential for the production of ethanol with yields (EtOHY) of 4.2 mmolEtOH.g-1COD (R6M) and 3.5 mmolEtOH.g-1COD (R2S). In the comparison between the two inocula used, both showed a balance in terms of hydrogen production, but in terms of ethanol production, the sludge from poultry slaughterhouse showed highest potential. By cloning and sequencing of the 16S rRNA gene for bacteria domain reactor R4S (whey), there was a predominance of the genus Selenomonas (69 % of the sequences) and Clostridium (8 % of the sequences). For the reactor R3M (glucose and cassava) analyzes cloning and sequencing of bacterial consortium revealed similarities with Lactobaccilus. As for the archaeal domain, the sequencing of the 16S rRNA gene had highly similar to the genus Methanobacterium (98.5 % and 95 % of the sequences), for R4S and R3M, respectively reactors. / O objetivo deste estudo foi avaliar a influência do tempo de detenção hidráulica (TDH), da origem de diferentes inóculos (lodo de suínos e lodo de aves), e da fonte de carbono (glicose, manipueira e soro de queijo) sobre a estabilidade e eficiência do reator anaeróbio de leito fluidizado (RALF) na produção de hidrogênio e etanol. Foram utilizados doze reatores idênticos, sendo que em dois reatores foram utilizados mistura de glicose com soro de queijo (R1S, R2S), seis reatores foram utilizados a mistura de água do processamento da mandioca (manipueira) e glicose (R1M, R2M, R3M e R4M). Também foi avaliado o uso individual do soro de queijo (R3S, R4S, R5S e R6S) e da manipueira (R5M e R6M). Os RALFs foram inoculados com lodo proveniente do tratamento de águas residuárias de suinocultura (R1S, R3S, R1M, R3M, R5S, R6S, R5M e R6M) e de águas residuárias do abatedouro de aves (R2S, R4S, R2M, R4M), ambos tratados termicamente. Foram realizadas variações de TDH (14-1 h) e concentrações de substrato (2- 15 g. L-1), com controle de temperatura a 30°C. Os reatores que utilizaram soro de queijo como substrato apresentaram um maior potencial para a produção de hidrogênio, com rendimentos (HY) de 3,2 mmolH2.g-1DQO (R6S) e 2,6 mmolH2.g-1DQO (R5S), por meio da aplicação de um TDH de 6 e 14 horas, com uma concentração de 3 e 5 g.L-1, respectivamente. Ambos os substratos apresentaram potencial para a produção de etanol, com rendimentos (EtOHY) de 4,2 mmolEtOH.g-1DQO (R6M) e 3,5 mmolEtOH.g-1DQO (R2S). Na comparação entre os dois inóculos utilizados, ambos apresentaram um equilíbrio em termos de produção de hidrogênio, porém em termos de produção de etanol, o lodo proveniente do abatedouro de aves apresentou um maior potencial. Por meio da clonagem e sequenciamento do gene RNAr 16S para o domínio bactéria do reator R4S (soro de queijo), houve a predominância do gênero Selenomonas (69% das sequências) e do gênero Clostridium (8% das sequências). Para o reator R3M (glicose e manipueira) as análises de clonagem e sequenciamento do consórcio bacteriano revelaram semelhanças com Lactobaccilus. Já para o domínio archaea, o sequenciamento do gene RNAr 16S, teve altas similaridades com gênero Methanobacterium (98,5% e 95% das sequências), para os reatores R4S e R3M, respectivamente.

Made available in DSpace on 2014-10-09T12:42:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:55Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:35:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:58Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP