Une étape clé du développement de nouveaux catalyseurs est l'évaluation de leurs performances. Les tests de catalyseurs sont généralement opérés dans des unités pilotes de "petite" taille dont les avantages sont une consommation moindre de réactif et un coût d'opération plus réduit. Les réacteurs d'unité pilote ont des diamètres de l'ordre de 3 à 10 fois la taille des catalyseurs qui sont généralement des sphères ou des cylindres dont la dimension typique est 2 à 3 mm. Des données expérimentales ont mis en évidence des difficultés de répétabilité des résultats sur certains réacteurs très courts. L’objectif de ce travail est de comprendre le lien entre la micro-structure de l’empilement, qui est aléatoire et localement hétérogène, l'hydrodynamique locale et la réactivité dans des réacteurs à lit fixe de petite taille, en vue de définir des critères de conception et des méthodologies de chargement permettant d'obtenir des performances chimiques répétables. La démarche retenue est purement numérique basée sur deux codes développés à IFPEN : Grains3D pour générer numériquement l'empilement et PeliGRIFF pour simuler l'écoulement réactif dans le lit fixe. Une analyse de l'état de l'art sur le sujet donne des informations abondantes sur les lits de particules sphériques, et très peu sur les cylindres, en particulier sur les couplages écoulements et transfert/réaction. En effet, ces travaux ne permettent pas de lier les performances réactives à la structure locale hétérogène de ces empilements. Dans ce travail, la caractérisation globale et locale d'empilements de sphères et de cylindres a permis de confirmer et compléter la littérature sur certains points : porosité au centre décrite de façon approximative par les corrélations, porosité axiale, orientations des cylindres... Des variations sont présentes à l’intérieur des lits de petite taille, variations qui ne s’atténuent pas avec l’augmentation du volume d’étude et qui sont équivalentes d’un chargement à l’autre. L'étude de l'hydrodynamique dans des lits de sphères et de cylindres mono- et polydisperses a également permis de quantifier l'effet de la répétition du chargement sur la perte de pression et les champs de vitesse. Les premiers résultats d'écoulement réactif ont montré que, qualitativement, le champ de concentration dans la particule réactive est sensible à l’écoulement en présence d'une limitation interne au transfert de matière. Ces résultats préliminaires ont permis de définir une méthodologie de travail qui pourra servir pour continuer l'étude. / The evaluation of catalyst performances is needed for their development. Catalytic tests are generally operated in pilot units of "small" size. Their advantages are : the reduction of reactant consumption and the reduction of operating costs. The pilot plant reactors have diameters of about 3 to 10 times the size of the catalyst (mainly spheres and cylinders) and the results obtained should be representative of the same performance of the catalysts in industrial units whose characteristic scale is around 5 meters. Experimental data have shown unacceptable repeatability in some small size reactors. The objective of this work is to understand the link between the local micro-structure of the packed bed, which is random and locally heterogeneous, local hydrodynamics and chemical responses in fixed bed reactors of small size. This study aims to define design criteria, and packing methodologies in order to obtain repeatable results. The approach adopted for this work is essentially based on numerical simulations. Two IFPEN codes are used for this study: Grains3D which is used to generate numerically the packed bed, and PeliGRIFF to simulate the reactive flow within the reactor. Previous works give information on packing, hydrodynamics and reactive flow characterization, mostly on spheres, much less is available on cylinders. However, they do not link local structure to reactive performance of the bed. In our work, geometrical characterization of the randomly packed beds of spheres and cylinders confirm and complete literature on several points: porosity at the centre of the reactor for which the correlations are inaccurate, the effect of bed height on the axial bed porosity, cylinder orientations... Some variations are present within small size beds, variations that are not dampened with an increase of averaging volume, and are similar from one packing to another. Hydrodynamics study carried out in packed beds of spheres and cylinders of different sizes allowed to link the packing local structure to pressure drop and velocity field. Only preliminary simulations have been performed on reactive flow. First qualitative results show an evolution of the concentration field inside pellets with flow in case of internal mass transfer limitations. Continuing these preliminary results will yield to the definition of a methodology that can be used to link local structure to reactive performance in randomly fixed packed bed reactors of small size.

O crescente aumento no uso de metais e outros produtos químicos nos processos industriais tem resultado na geração de grandes quantidades de efluentes aquosos que contém altos níveis de metais tóxicos, o que gera sérios problemas ambientais associados ao descarte destes efluentes. O objetivo deste trabalho foi realizar uma investigação da biossorção do íon manganês II de uma solução aquosa utilizando a biomassa seca Sargassum filipendula. O processo foi conduzido em batelada com um posterior estudo dinâmico do processo em regime contínuo em um reator de leito fixo. No processo em batelada, a influência de diferentes parâmetros experimentais foram avaliados: pH inicial, tempo de biossorção, temperatura e concentração inicial do íon manganês II no equilíbrio de biossorção do sistema. No processo em regime contínuo, foi utilizada uma coluna de leito fixo, sendo avaliados os seguintes parâmetros: vazão de alimentação e concentração inicial de manganês II em solução. Os resultados obtidos indicam que a capacidade de biossorção não foi afetada pelo pH na faixa de 3,0 a 7,0, mas diminuiu de modo significativo para pH inferior a 3,0. A isoterma de Langmuir foi a que melhor descreveu o equilíbrio de biossorção, que foi pouco afetado pela temperatura. O processo de biossorção obedeceu a uma cinética de pseudo segunda-ordem, cuja taxa também não sofreu efeito significativo da temperatura. Os resultados obtidos nos estudos em batelada indicam que a Sargassum filipendula possui potencial para a remoção de íons manganês, apresentando capacidade de adsorção igual a 0,80 mmol/g, valor comparável àqueles observados para outros íons tóxicos. Os valores para capacidade de biossorção calculados no sistema contínuo foram superiores aos encontrados para o estudo em batelada, o que foi associado às diferentes condições de equilíbrio existentes nos dois sistemas. O processo de biossorção do manganês em leito fixo, mostrou-se eficiente para concentrações iniciais do efluente menores que 500 mg/L. Para uma concentração inicial de 60 mg/L, com 9 horas de processo o ponto de ruptura foi alcançado, 26 L de solução foram tratados de acordo com a concentração exigida pelo CONAMA para o despejo em um corpo receptor. / The increasing use of metals and other chemicals in industrial processes has resulted in the generation of large quantities of aqueous effluents containing high levels of toxic metals, which cause serious environmental problems associated with the disposal of effluents. This work was doing a research on removing manganese II ions of an aqueous solution using the dry biomass Sargassum filipendula. A basic investigation on the removal of manganese II ions from aqueous solutions by dead Sargassum filipendula was conducted in batch and in a fixed- bed column. The influence of different experimental parameters was evaluated in batch conditions: initial pH, sorption time, temperature, and initial concentrations of manganese II ions on metal uptake. Continuous-flow sorption experiments were conducted in a fixed-bed column. The parameters evaluated were: effluent flow rate and initial concentration of manganese II solution. The results indicate that the metal uptake capacity was not affected by pH in the range of 3.0 to 7.0, but decreased significantly to less than pH 3.0. The equilibrium biosorption was better described by Langmuir isotherm, which was little affected by temperature. The process of biosorption followed the kinetics of a pseudo-second order, whose rate also has not suffered significant effect of temperature. The results obtained in a batch studies indicate that the Sargassum filipendula has potential for the removal of manganese ions, its maximum uptake capacity equal 0.80 mmol/g, a result comparable to those observed for other toxic ions. The results for capacity of biosorption calculated in continuous system were higher than those found in batch for the study, which was associated with the different conditions of balance in the two existing systems. The process of biosorption of manganese in fixed-bed reactor, has proved effective for initial concentrations lower than 500 mg/L. For an initial concentration of 60 mg/L, with nine hours to process the breaking point was reached, 26 L of solution were treated in accordance with the concentration required by CONAMA for emptying into a body receiver.

Ce travail s'inscrit dans le cadre Power-to-Gas, dont l'objectif est de stocker les surplus d'énergie électrique issus de sources renouvelables sous forme d'énergie chimique, en l'occurrence le méthane. L'intermittence de la production électrique requiert une certaine flexibilité du système de méthanation par rapport aux variations temporelles de conditions opératoires. Dans ce contexte, les travaux effectués au cours de cette thèse sont dédiés à l'étude du comportement dynamique d'un réacteur-échangeur de méthanation à lit fixe catalytique. Une maquette de réacteur finement instrumentée en thermocouples est conçue et permet l'étude expérimentale des performances du réacteur et de son comportement thermique en régime dynamique. En particulier, des phénomènes de fronts d'onde thermique, de dépassements et de réponses inverses sont retrouvés. Les paramètres hydrodynamiques et thermiques du lit ont été caractérisés expérimentalement. Une modélisation de la maquette de réacteur-échangeur est également établie et permet de simuler son fonctionnement. Les résultats expérimentaux sont comparés aux résultats de simulation, permettant l'analyse précise des comportements observés dans le réacteur / This work is within the Power-to-Gas framework, which aims to store the electrical energy surpluses from renewable energy in chemicals, here the methane. The intermittency of the electrical production requires the methanation system to have a certain level of flexibility with respect to temporal changes of operational conditions. In this context, the work carried out during this thesis is dedicated to the study of the dynamic behavior of a catalytic fixed-bed heat-exchanger methanation reactor. A reactor-exchanger highly equipped with thermocouples is designed and is used for the experimental study of the performances and the dynamics behavior of such a reactor. In particular, phenomena of thermal wave fronts, overshoot and inverse responses are found. The hydrodynamic and thermal parameters of the bed have been experimentally characterized. Modeling of the reactor-exchanger is also established and simulations of the reactor behavior are done. The experimental results are compared with the simulation results, allowing the precise analysis of the behaviors observed in the reactor

O crescente aumento no uso de metais e outros produtos químicos nos processos industriais tem resultado na geração de grandes quantidades de efluentes aquosos que contém altos níveis de metais tóxicos, o que gera sérios problemas ambientais associados ao descarte destes efluentes. O objetivo deste trabalho foi realizar uma investigação da biossorção do íon manganês II de uma solução aquosa utilizando a biomassa seca Sargassum filipendula. O processo foi conduzido em batelada com um posterior estudo dinâmico do processo em regime contínuo em um reator de leito fixo. No processo em batelada, a influência de diferentes parâmetros experimentais foram avaliados: pH inicial, tempo de biossorção, temperatura e concentração inicial do íon manganês II no equilíbrio de biossorção do sistema. No processo em regime contínuo, foi utilizada uma coluna de leito fixo, sendo avaliados os seguintes parâmetros: vazão de alimentação e concentração inicial de manganês II em solução. Os resultados obtidos indicam que a capacidade de biossorção não foi afetada pelo pH na faixa de 3,0 a 7,0, mas diminuiu de modo significativo para pH inferior a 3,0. A isoterma de Langmuir foi a que melhor descreveu o equilíbrio de biossorção, que foi pouco afetado pela temperatura. O processo de biossorção obedeceu a uma cinética de pseudo segunda-ordem, cuja taxa também não sofreu efeito significativo da temperatura. Os resultados obtidos nos estudos em batelada indicam que a Sargassum filipendula possui potencial para a remoção de íons manganês, apresentando capacidade de adsorção igual a 0,80 mmol/g, valor comparável àqueles observados para outros íons tóxicos. Os valores para capacidade de biossorção calculados no sistema contínuo foram superiores aos encontrados para o estudo em batelada, o que foi associado às diferentes condições de equilíbrio existentes nos dois sistemas. O processo de biossorção do manganês em leito fixo, mostrou-se eficiente para concentrações iniciais do efluente menores que 500 mg/L. Para uma concentração inicial de 60 mg/L, com 9 horas de processo o ponto de ruptura foi alcançado, 26 L de solução foram tratados de acordo com a concentração exigida pelo CONAMA para o despejo em um corpo receptor. / The increasing use of metals and other chemicals in industrial processes has resulted in the generation of large quantities of aqueous effluents containing high levels of toxic metals, which cause serious environmental problems associated with the disposal of effluents. This work was doing a research on removing manganese II ions of an aqueous solution using the dry biomass Sargassum filipendula. A basic investigation on the removal of manganese II ions from aqueous solutions by dead Sargassum filipendula was conducted in batch and in a fixed- bed column. The influence of different experimental parameters was evaluated in batch conditions: initial pH, sorption time, temperature, and initial concentrations of manganese II ions on metal uptake. Continuous-flow sorption experiments were conducted in a fixed-bed column. The parameters evaluated were: effluent flow rate and initial concentration of manganese II solution. The results indicate that the metal uptake capacity was not affected by pH in the range of 3.0 to 7.0, but decreased significantly to less than pH 3.0. The equilibrium biosorption was better described by Langmuir isotherm, which was little affected by temperature. The process of biosorption followed the kinetics of a pseudo-second order, whose rate also has not suffered significant effect of temperature. The results obtained in a batch studies indicate that the Sargassum filipendula has potential for the removal of manganese ions, its maximum uptake capacity equal 0.80 mmol/g, a result comparable to those observed for other toxic ions. The results for capacity of biosorption calculated in continuous system were higher than those found in batch for the study, which was associated with the different conditions of balance in the two existing systems. The process of biosorption of manganese in fixed-bed reactor, has proved effective for initial concentrations lower than 500 mg/L. For an initial concentration of 60 mg/L, with nine hours to process the breaking point was reached, 26 L of solution were treated in accordance with the concentration required by CONAMA for emptying into a body receiver.

Submeteu-se um Reator Anaeróbio Horizontal de Leito Fixo (RAHLF) de bancada, ao aumento progressivo da concentração de matéria orgânica afluente, e a cargas de choque orgânicas, com o objetivo de verificar-se seu desempenho e estabilidade operacional. O RAHLF foi construído com um tubo de boro-silicato de 100 cm de comprimento, 5,0 cm de diâmetro e 1995 ml de volume total e preenchido com lodo anaeróbio imobilizado em matrizes de espuma de poliuretano. O reator foi alimentado, inicialmente, com substrato composto principalmente de carboidratos em concentrações, expressas como Demanda Química de Oxigênio (DQO) de, aproximadamente, 200, 1000 e 2000 mg/l. Posteriormente, os carboidratos foram substituídos por metanol e ácidos voláteis, em concentrações totais, aproximadas, de 2000, 3000, 4000 e 5000 mg DQO/l. Atingido o estado estacionário para cada condição operacional, foram aplicadas cargas de choque, aumentando-se em três vezes o valor da DQO afluente, durante período equivalente ao tempo de detenção hidráulica (sete horas). O sistema apresentou problemas operacionais durante os experimentos com carboidratos, quando submetido a 2000 mg DQO/l, correspondente à taxa volumétrica de carregamento orgânico de 8,77 KgDQO/m3.d. Não foi verificado qualquer problema operacional durante os experimentos com substrato contendo metanol e ácidos voláteis, e o reator apresentou eficiência de remoção de DQO superior a 90%. Para o experimento com DQO afluente igual a 2000 mg/l, os parâmetros cinéticos foram estimados a partir de modelo cinético de 1ª ordem, obtendo-se valor de k1 igual a 0,049 h-1, nos demais experimentos ajustou-se modelo cinético de 2ª ordem com valor médio de k2 equivalente a 2,0 x 10-4 l/mg.h Foram aplicadas cargas de choque orgânicas equivalentes a, aproximadamente, 17; 27; 40 e 47 kgDQO/m3.d. Os efeitos das sobrecargas orgânicas no reator foram transientes em todos os casos, tendo o reator voltado à condição inicial em, no máximo, 15 horas após o início das sobrecargas. / A Horizontal flow Anaerobic lmmobilized Sludge Reactor (HAIS) was subjected to progressively increasing concentrations of organic effluent material and to organic shock loads with the purpose of investigating its operational performance and stability. The HAIS, consisting of a 100 cm long, 5 cm diameter borosilicate tube with a total volume capacity of 1995 mL, was filled with anaerobic sludge immobilized in foam and polyurethane matrixes. The reactor was initially fed with a substrate composed mainly of carbohydrates in concentrations, expressed as Chemical Oxygen Demand (COD), of approximately 200, 1000 and 2000 mg/L. These carbohydrates were later replaced by methanol and volatile acids in total concentrations of 2000, 3000, 4000 and 5000 mg COD/L. Shock loads were applied after each operational condition became stationary, with the effluent COD tripled for a period equivalent to the hydraulic detention time (seven hours). The system presented operational problems during the experiments with carbohydrates when subjected to 2000 mg DQO/l, which corresponded to a volumetric organic load index of 8,77 Kg COD/m3.d. No operational problems were detected during the experiments with substrates containing methanol and volatile acids, and the reactor presented a COD removal efficiency of over 90%. The kinetic parameters for the COD effluent with 2000 mg/L were estimated based on a first arder kinetic model, which resulted in a k1 value of 0,049 h-1, while a kinetic model of the second order was used for the remaining experiments, with a mean value of k2 equivalent to 2,0 x 10-4 L/mg.h. Organic shock loads of approximately 17; 27; 40 and 47 kg COD/m3.d were applied. The effects of the organic overloads on the reactor were transient in every case, with the reactor returning to its initial condition at the most 15 hours after the beginning of the overloads.

Este trabalho apresenta as avaliações de desempenho, das demandas operacionais e dos fatores intervenientes no aumento da escala da unidade piloto do Reator anaeróbio Horizontal de Leito Fixo (RAHLF) no tratamento de esgoto sanitário após passagem por peneira com malha de 1 mm, durante dois anos de operação. O reator dispunha de volume total de 237,5 1, construídos com tubos comerciais de PVC de 14,5 cm de diâmetro (D), dispostos em cinco módulos horizontais em série de 2,88 m, perfazendo um comprimento total de (L) de 14,4 m e relação de total de L/D de 100. O suporte de imobilização de biomassa, espuma de poliuretano em matrizes cúbicas de 1 cm de aresta, mostrou-se adequado ao desenvolvimento do biofilme. Em partida, sem inoculação prévia, ocorreu a sua consolidação a partir de 70 dias, com predominância de morfologia semelhante a Methanosaeta sp. em relação a da Methanosarcina. Em torno de 90 dias com afluente de 350 mg/l de DQO, observe-se a melhor qualidade do efluente, com valor de 100 mg/l de DQO. Em longa operação ocorreu queda de rendimento e menor reprodutibilidade das previsões do projeto, atribuída aos constantes entupimentos e ineficácia das operações de limpeza, com o comprometimento de volume reacional verificados por estudos de hidrodinâmica. Da investigação das origens dos equipamentos observou-se tratar mais de um efeito local e qualitativamente relacionado à biomassa retida que propriamente quantitativo e extensivo ao longo de todo reator, com produção continuada de polímeros extracelulares, promovendo um efeito sinérgico com os predominantes organismos filamentosos e com os sólidos particulados retidos no leito. Diante das potencialidades desta configuração de reator apontam-se alternativas de mitigação dos entupimentos e o direcionamento dos estudos necessários para novo aumento de escala para o tratamento de esgoto sanitário. / This work evaluated the performance, the operational demands and the intervenient factors in the scale-up of the horizontal flow anaerobic immobilized biomass (HAIB) reactor pilot unit, treating domestic sewage previously screened. The operation was monitored for two years. The five- module (2.88 m length each) reactor volume was 237.5 liters and it was built with commercial PVC pipes of 14.5 cm of diameter (D), resulting in a total length (L) of 14.4 m and in a total ratio L/D of approximately 100. The immobilization support, cubic matrices of polyurethane foam (1 cm edge), showed to be suitable for the anaerobic biofilm development. During the start-up, without previous inoculation, the biofilm seemed to be consolidated after 70 days, and Methanosaeta sp. morphology predominated, in detriment of Methanosarcina. With an affluent of 350 mg COD/L, the best reactor performance was observed in about 90 days of operation (100 mg COD/L in the effluent). However, with the continuous operation, its performance decreased and the project predictions did not seem to fit anymore. These facts were probably due to the frequent cloggings ant the inefficiency of the backwashing procedures, leading to a decreasing of the operational volume. The origin of the clogging seemed to be related to the extracellular polymer production, linked to a synergic effect with the filamentous organisms and the particulate solids in the bed. Despite these operational problems, there were found alternatives to mitigate the clogging, and studies about a new scale-up methodology, in order to treat domestic sewage, were strongly recommended.

O projeto consistiu na concepção e avaliação do desempenho de um sistema anaeróbio-aeróbio para tratamento de esgoto sanitário. O leito do reator foi dividido em quatro compartimentos de igual volume. Foi usada espuma de poliuretano para imobilização da biomassa e, para facilitar a partida do reator, esse material suporte foi previamente inoculado. O projeto teve três fases distintas: na primeira etapa, foi observada a importância da concentração de biomassa anaeróbia no desempenho de reator anaeróbio a princípio operado com metade do leito reacional com espuma e, a seguir, com o leito todo preenchido com espuma. Na segunda etapa, foram testados diferentes tempos de detenção hidráulica no reator que operou apenas em condições anaeróbias. Na última etapa foi operado o reator combinado anaeróbio-aeróbio. Ficou constatada a importância da concentração de microrganismos no desempenho do reator anaeróbio, pois com o aumento da quantidade de espuma, o reator atingiu resultados melhores e maior estabilidade operacional. Foi comprovada a influência do tempo de detenção hidráulica (TDH) no desempenho do reator. Tempos de detenção muito altos acarretam problemas de transferência de massa líquido-sólido, e baixos TDH dificultam adequada ação dos microrganismos. O melhor resultado para o reator em operação exclusivamente anaeróbia foi para o TDH de 10 horas, no qual se conseguiu reduzir a DQO de amostra bruta de 389 +/- 70 mg/L para 137 +/- 16 mg/L, em média. Para o reator operado anaeróbio-aeróbio a DQO de amostra bruta decresceu de 259 +/- 69 mg/L para 93 +/- 31 mg/L, em média. A comparação de todos os resultados obtidos, evidenciou a importância do pós-tratamento aeróbio na remoção de parcela de matéria orgânica não removida em tratamento unicamente anaeróbio. / The project consisted in the design and performance evaluation of an anaerobic-aerobic system for wastewater treatment. Polyurethane foam was used for biomass immobilization and, to smooth the reactor start-up, this supporting material was previously inoculated. The project was divided in three distinct phases. In the first one, the importance of the anaerobic biomass concentration was observed in the performance of the anaerobic reactor in a way to operate the reactor primarily with half of the reaction bed filled with foam and subsequently operate it with the bed completely filled with foam. In the second phase, different times of hydraulic retention were tested with the reactor operating exclusively in anerobic conditions. In the third and last phase, an anaerobic-aerobic combined reactor was operated. It was possible to confirm the importance of microorganism concentration in the performance of the anaerobic reactor, since the increase in the amount of foam allowed the reactor to reach better results and greater operational stability. The influence of the hydraulic retention time in the reactor performance was also proved. Very high retention times cause problems in the liquid-solid mass transference, while low retention times do not allow an adequate action of microorganisms. The best result for the reactor with an exclusive anaerobic operation was the 10 hour retention time, when it was possible to reduce the COD of a 389 +/- 70 mg/L gross sample to a 137 +/- 16 mg/L in average. On the other hand, for the anaerobic-aerobic operating reactor, the COD of a gross sample dropped from 259 +/- 69 mg/ L to 93 +/- 31 mg/L in average. Finally, comparing all the obtained results, it was possible to verify the importance of the anaerobic post treatment in the removal of a part of the organic matter not removed in an exclusively anaerobic treatment.

A atividade industrial diversificada tem sido responsável pelo lançamento, no ambiente, de resíduos que contém materiais tóxicos e/ou de difícil degradação. Benzeno, tolueno, etilbenzeno e xilenos (BTEX) são compostos importantes, por estarem presentes em águas superficiais e subterrâneas, geralmente a partir de contaminações por derivadas de petróleo. Enquanto a degradação aeróbia de BTEX já está amplamente entendida e descrita, a aplicação de processos anaeróbios de tratamento, indicados na década de 80 ainda requer mais estudos. Reatores anaeróbios horizontais de leito fixo de bancada preenchidos com cubos de espuma de poliuretano, contendo lodo anaeróbio proveniente de diversas fontes trataram a água residuária sintética a base de proteínas, carboidratos, lipídios, contendo solução etanólica de BTEX e solução de BTEX em detergente comercial; e solução etanólica de BTEX como únicas fontes de carbono. A influência da adição de nitrato e sulfato como aceptores de elétrons na degradação anaeróbia também é discutida. Os reatores foram capazes de remover BTEX nas concentrações testadas de até 15,0 mg/L de cada composto, com tempos de detenção hidráulica de 11,4 horas e 13,5 horas. Os reatores forneceram condições excelentes para o desenvolvimento de biofilme complexo capaz de degradar BTEX, contendo organismos degradadores de BTEX, acetogênicos, acetoclásticos e hidrogenotróficos. Arqueas metanogênicas representaram menos de 0,5% do total de organismos anaeróbios na biomassa dos reatores. O modelo cinético de primeira ordem com residual foi o que melhor representou os dados experimentais e as velocidades de degradações de BTEX, estimadas neste trabalho, foram cerca de 10 a 94 vezes maiores que as encontradas na literatura, em ensaios realizados em microcosmos. / The diversified industrial activity has been responsible for discharge in the environment of toxic and/or difficult degradation compounds. Benzene, toluene, ethylbenzene and xylenes (BTEX) are important compounds present in surface and ground waters, usually from petroleum products contamination. While BTEX aerobic degradation is extensively understood and described, anaerobic treatment application, started in the eighties, associated to fundamental studies need to be improved. Bench-scale horizontal-flow anaerobic immobilized biomass reactors filled with polyurethane foam matrices, containing immobilized anaerobic biomass from various sources, treated synthetic substrate containing protein, carbohydrates, lipids, BTEX solution in ethanol and BTEX solution in commercial detergent, as well as BTEX solution in ethanol as the sole carbon source. The influence of the addition of nitrate and sulfate as electron acceptors on anaerobic degradation is also discussed. The reactors were able to remove up to 15.0 mg/L of each BTEX compound, with hydraulic detention time of 11.4 hours and 13.5 hours. The reactors provided excellent conditions for developing a complex biofilm with BTEX-degraders, acetogenic, acetoclastic and hydrogenotrophic microorganisms. Methanogenic archaea were found to represent less than 0.5% of the total anaerobic organisms in the biomass inside the reactors. Residual first order kinetic model fitted well the experimental data and the BTEX degradation rates, estimated in this work, were about 10- to 94-fold higher than those found in the literature, in microcosms studies.

Les procédés actuellement utilisés à bord de la Station Spatiale Internationale permettent un traitement physico-chimique des déchets avec un recyclage partiel des éléments en minimisant le réapprovisionnement en eau et oxygène. Voyager plus loin et sur de plus longues durées n’est possible que si un système de support de vie, permettant d’assurer une autonomie plus importante, est mis en place. Le projet MELiSSA est un système de support de vie biorégénératif ayant pour objectifs de recycler les déchets produits par l’homme, de régénérer l’oxygène et l’eau et d’assurer une production de nourriture. L’utilisation de microorganismes pour assurer ces différentes fonctions, n’est réalisable qu’en ayant la meilleure connaissance possible et surtout la maîtrise des processus et des souches impliqués. L’objectif de cette thèse est de développer un modèle prédictif pour le compartiment nitrificateur de la boucle MELiSSA. Dans un premier temps, les souches Nitrosomonas europaea ATCC® 19718 et Nitrobacter winogradskyi ATCC® 25391 ont été étudiées et ont permis de définir un modèle cinétique de ces deux bactéries en culture immergée. Dans un second temps, ce modèle a été combiné à un modèle N-bacs en série pour composer un modèle de nitrification dans une colonne à lit fixe à biomasse fixée : le modèle NitriSim. Ce modèle a été testé sur une expérience de long-terme menée dans une colonne à lit fixe dont le support est composé de billes Biostyr®. Le dernier chapitre de ce manuscrit décrit l’utilisation d’une souche dégradant l’urée, Cupriavidus pinatubonensis, dans le réacteur à lit fixe. Les différents résultats ont permis de définir un modèle de nitrification dans un réacteur à lit fixe et de présenter des perspectives possibles pour le traitement de l’urine au niveau du compartiment nitrifiant de MELiSSA. / Physico-chemical processes are used on the International Space Station for partial recycling of wastes in order to minimize the resupplies of oxygen and water. Further and longer explorations can only be possible if a life support system is applied to enhance autonomy to the station. MELiSSA is a biological life support system project aiming for waste recycling, water and air regeneration and production of simple food. The only way to assure these functions is the use of microorganisms which is requiring a high knowledge and a perfect control of processes implicated. The thesis objectives consist in developing a predictive model for the MELiSSA nitrifying compartment. First, a kinetic study of Nitrosomonas europaea ATCC® 19718 and Nitrobacter winogradskyi ATCC® 25391 in submerged bioreactors allowed defining a kinetic model of nitrification. Secondly, this model was combined to an N-tanks in series one to compose a nitrification model in fixed-bed biorectors : NitriSim. It was applied on a long-term experiment in a fixed-bed bioreactors where the bed was composed of Biostyr® beads. The last part of this work was about the use of a urea-degradating bacteria, Cupriavidus pinatubonensis, in the fixed-bed bioreactor. All of these results leaded to the development of a nitrification in fixed-bed reactors model and opened up interesting prospects for the urine degradation in the nitrifying compartment of MELiSSA.

Die vorliegende Arbeit beschäftigt sich mit rohstofflichen und verfahrenstechnischen Einflussfaktoren bei der Biomassepyrolyse. Ausgehend von der Entwicklung einer kleintechnischen Festbettpyrolyseapparatur, erfolgten experimentelle Untersuchungen an 26 biogenen Einsatzstoffen unter verschiedenen Prozessbedingungen. Die Apparatur erlaubt eine vollständige Bilanzierung und Gewinnung aller Produkte, zudem können Einflüsse durch sekundäre Reaktionen in der Gasphase minimiert werden. Die Einsatzstoffe, welche u. a. auch Zellstoff, Xylan und Alkali-Lignin einschließen, wurden hinsichtlich brennstofftechnischer und physikalischer Eigenschaften sowie der Stoffgruppenzusammensetzung charakterisiert. Sie repräsentieren eine große Bandbreite möglicher Zusammensetzungen. Bei den Prozessparametern wurde die Pyrolysetemperatur im Bereich von 200 bis 750 °C, die Aufheizrate zwischen 5 und 100 K/min, die Feststoffverweilzeit von 0 bis 30 min sowie die Partikelgröße (0 bis 5 mm) variiert. Aus den Untersuchungen zum Einfluss der Prozessparameter für die verschiedenen Einsatzstoffe wurden unter Anwendung einer geeigneten Bilanzierungsmethodik geschlossene Masse- und Elementbilanzen für jeden Versuchspunkt aufgestellt. Unter den Prozessvariablen konnte die Temperatur erwartungsgemäß als wichtigste Einflussgröße identifiziert werden. Der zweistufige Zersetzungsverlauf der Biomassen ermöglicht die mathematische Beschreibung der temperaturabhängigen Ausbeuten mittels der zweistufigen Boltzmann-Funktion für den gesamten Temperaturbereich mit hohen Bestimmtheitsmaßen. Die rohstofflichen Einflussgrößen wurden unter Anwendung der Rangkorrelationsmethode nach Spearman und der Produkt-Moment-Korrelation nach Pearson mit den definierten Zielgrößen (Ausbeuten, Produktzusammensetzung, Kokseigenschaften, Heizwerte, Energieeinbindung) bei verschiedenen Pyrolysetemperaturen korreliert. Neben der Stoffgruppenzusammensetzung konnten bei den rohstofflichen Einflussfaktoren die Gehalte an Alkalien sowie der Gesamtgehalt an potentiell katalytisch aktiven Bestandteilen (Na, K, Mg, Ca, Fe) als Haupteinflussgrößen identifiziert werden. Korrelationen ergeben sich auch für brennstofftechnische Eigenschaften, wobei neben dem Flüchtigen- und dem Aschegehalt, das O/C-Verhältnis signifikant ist. Die gefundenen statistischen Zusammenhänge können weitestgehend mechanistisch begründet werden. Zur Quantifizierung der ermittelten Zusammenhänge für die Zielgrößen wurden multiple Regressionsmodelle erstellt und anhand von Bestimmtheitsmaß, Informationskriterium und mittleren Modellfehlern bewertet. Somit konnten 42 Regressionsgleichungen für die Produktausbeuten bei verschiedenen Pyrolysetemperaturen entwickelt werden, die auf den Gehalten verschiedener Stoffgruppen und dem Gesamtgehalt an katalytisch aktiven Elementen basieren. Weitere 56 Regressionsgleichungen stehen für die Berechnung von Teer/Öl-Elementarzusammensetzung, Kokszusammensetzung, Teer/Öl-Heizwert sowie Energieeinbindung im Koks bei verschiedenen Pyrolysetemperaturen zur Verfügung. Die Prognoseeignung der Gleichungen wurde anhand eines weiteren Datensatzes für Apfeltrester überprüft. Für die Koks-, die Gas- und die Kondensatausbeute sowie die genannten Produkteigenschaften ergab sich eine gute Vorhersagequalität, die jedoch stark von der verwendeten Gleichung abhängt. Die Validierung mit Literaturdaten konnte aufgrund fehlender Datensätze, die sowohl die notwendigen Rohstoffparameter als auch Produktausbeuten und -eigenschaften enthalten, nur anhand der Koksausbeute erfolgen. Für verschiedene Biomassen und biogene Reststoffe führte dies zu einer guten Anpassung. Die mathematische Beschreibung der Ausbeuten und bestimmter Produkteigenschaften über Regressionsgleichungen auf Grundlage von Rohstoffparametern stellt einen vielversprechenden Ansatz für die Vorhersage der maximalen Ausbeuten bei bestimmten Bedingungen dar. Dies ermöglicht eine Abschätzung zur Einsatzeignung von Biomassen bzw. biogenen Reststoffen für verschiedene Anwendungszwecke. Bisher existiert kein derartiges Modell zur Vorhersage der definierten Zielgrößen. Grundsätzlich wäre die Entwicklung einfacher Gleichungen mit wenigen, einfach bestimmbaren und standardisierten Parametern erstrebenswert. Die Ergebnisse haben jedoch gezeigt, dass Ein-Variablen-Modelle die Trends zwischen den Biomassen aufgrund der komplexen Zusammenhänge zwischen Pyrolyseverhalten und Rohstoffparametern häufig nicht richtig wiedergeben können. Für robuste Modelle sind somit mindestens zwei unabhängige Modellparameter mit idealerweise gegensätzlichem Einfluss notwendig. / The intention of this work was an intensive study of the influence of feedstock properties and process variables on biomass pyrolysis. Due to a lack in consistent data sets, including various feedstock parameters as well as product yields, compositions, and further properties, a laboratory fixed bed reactor was developed to overcome this problem. The pyrolysis reactor was used for experiments with 26 biogenous feedstock under variable process conditions. The reactor is suitable to assure nearly closed mass balances and a complete product recovery. Furthermore, it allows the minimization of secondary reactions. The used feedstock, which include cellulose, xylan, and lignin amongst others, represent a broad range of possible compositions and were intensively characterized by determination of fuel and physical properties as well as biopolymer composition. The varied process parameters are: temperature between 200 and 700 °C, heating rate in the range of 5 to 100 K/min, solid residence time from 0 to 30 min, and particle size up to 5 mm. Closed mass and element balances were done for every set of parameters. As expected, amongst process variables the temperature was identified as the main factor influencing biomass pyrolysis. The temperature depending products yields could be fitted well by the double boltzmann approach due to the two-stage pyrolytic decomposition of biomass. Correlation of feedstock properties with different target parameters, including yields, product composition, heating values, remaining energy content in char, and char properties, was done by Spearman´s rank correlation and Pearson´s correlation for different temperatures. Biopolymer composition as well as alkaline content and total content of potential catalytic elements (Na, K, Ca, Mg, Fe) were identified as main factors influencing biomass pyrolysis product yields and compositions. Further correlations arise with fuel properties like volatile matter and ash content besides O/C atomic ratio. The obtained correlations can be mainly related to pyrolysis mechanisms. The received relationships were quantified by means of multiple regression models. Model evaluation was done by coefficient of determination, information criteria and mean squared errors. 42 regression models, based on different biopolymer contents and the total content of catalytic elements, were provided for the mathematical description of product yields for different process temperatures. Another 56 equations are suitable for the calculation of product properties like tar/oil and char composition, tar/oil heating value, and remaining energy content in the char at different temperatures. The predictability of the regression models was proved using another data set for apple pomace. The yields of char, gas, and condensate as well as the aforementioned product properties can be predicted very well, although, the predictability varies with the applied equation. Validation of the models by literature data was only possible for the char yield, because of the mentioned lack in suitable and complete data sets. Application of regression model to fixed bed char yields for different biomass and biogenous residues from literature resulted in a good predictability. Mathematical description of pyrolysis product yields and properties by means of regression models based on feedstock parameters is a promising approach to predict maximum yields at defined conditions and, therefore, to make an estimation of suitability of the biomass to different applications. Up to now such models do not exist. In general, the development of simple equations based on a few standardized parameters which are easy to determine is worthwhile. Hence, the results showed that the overall trend between different biomass feeds was often not predicted correctly using one-parameter models. This is due to the complex relationships between pyrolysis behavior and feedstock properties. Consequently, at least two parameter models, where the variables show the opposite trends, were most appropriate.