A presente pesquisa teve por objetivo avaliar a produção biológica de hidrogênio em longo prazo, e os impactos da separação das principais etapas da digestão anaeróbia, acidogênese e metanogênese, sobre a eficiência do tratamento em reatores de leito fixo estruturado e sobre o desempenho da filtração em biorreatores com membrana. O efluente utilizado foi à base de sacarose e a temperatura foi mantida em 30ºC. Na primeira etapa experimental, avaliou-se a produção de H2 em três configurações de reatores: leito fixo estruturado (FB), UASB granular (UG) e UASB floculento (UF-1). Na segunda etapa experimental, um reator UASB acidogênico (UF-2) foi combinado a um reator metanogênico de leito fixo estruturado (RM). Um reator de estágio único de leito fixo estruturado (RU) foi operado em paralelo. Na última etapa experimental, foram avaliados dois biorreatores anaeróbios conjugados com módulos externos de membranas tubulares, nomeadamente 1-AnMBR, que foi alimentado com efluente bruto, e 2-AnMBR, que foi alimentado com efluente acidificado. Na primeira etapa, sob um TDH de 3,3 h (COV = 33 gDQO.L-1d-1), os reatores FB, UG e UF-1 apresentaram produção de H2 contínua, porém instável, com rendimentos de aprox. 1,5, 0,8 e 1,2 molH2.mol-1sacaroseconsumida, respectivamente. O reator UF-1 apresentou uma estabilidade relativamente melhor e, por isso, esta configuração foi utilizada nos experimentos seguintes. No reator UF-2, aumentou-se o TDH para 4,6 h (COV = 25 gDQO.L-1d-1), o que significativamente promoveu a melhoria do desempenho. Nenhum alcalinizante foi adicionado e o pH do efluente permaneceu em torno de apenas 2,7. Contudo, uma produção de H2 contínua, estável e por longa duração foi atingida, de 175 mLH2.L-1h-1 (= 4,2 LH2.L-1d-1), com rendimento de 3,4 molH2.mol-1sacaroseconsumida, concomitante com a produção de ácido acético e etanol. Nos reatores metanogênicos, o TDH aplicado foi gradativamente reduzido (53-18 h no RM e 56-23 h no RU). Após os sistemas atingirem estabilidade, os valores de DQO permaneceram inferiores no efluente do RM, sobretudo pela redução da concentração de SSV, equivalente a 92 mg.L-1, enquanto que no RU essa concentração foi de 244 mg.L-1. No final da operação, o rendimento energético do sistema de dois estágios foi de 20,69 kJ.g-1DQOadicionada, sendo 90% proveniente do CH4 e 10% do H2. Este rendimento foi 34% maior do que o obtido no reator de estágio único, que foi de 15,48 kJ.g-1DQOadicionada. Por fim, avaliando-se o desempenho da filtração nos biorreatores com membrana, verificou-se que a permeabilidade operacional foi, na maior parte do tempo, superior no 2-AnMBR. A pré-acidificação do efluente levou à redução de cerca de 56-59% na concentração de sólidos voláteis suspensos e totais no 2-AnMBR e à modificação no perfil do tamanho das partículas. No 1-AnMBR, porém, não havia partículas de pequenas dimensões, tais quais encontradas no reator acidogênico, indicando reduzido crescimento suspenso de bactérias acidogênicas. Embora os valores de fluxo crítico tenham sido muito semelhantes para ambos os AnMBR, testes de resistência específica da torta indicaram maior resistência do lodo do 1-AnMBR (1,02 x 1018 m-1), comparado ao lodo do 2-AnMBR (1,03 x 1012 m-1) e ao lodo acidogênico (7,44 x 1011 m-1). Portanto, essa pesquisa demonstrou, por meio da aplicação do tratamento anaeróbio em dois estágios, a viabilidade da produção contínua de hidrogênio em pH extremamente ácido e com mínimos requerimentos operacionais, a redução da concentração de sólidos suspensos no efluente de reatores de leito fixo estruturado, o potencial de aumento da recuperação de bioenergia e de redução da incrustação em membranas de ultrafiltração. / This study assessed long-term hydrogen production and the impacts of separating the main stages of anaerobic digestion (acidogenesis and methanogenesis) on treatment efficiency in structured fixed-bed reactors and on filtration performance in anaerobic membrane bioreactors. Sucrose based wastewater was used and the temperature was maintained at 30°C. In the first experimental phase, H2 production was evaluated in three different acidogenic reactors: structured fixed-bed (FB), granular UASB (UG) and flocculated UASB (UF-1). In the second experimental phase, an acidogenic UASB reactor (UF-2) was combined with a structured fixedbed methanogenic reactor (RM). A single-stage structured fixed-bed reactor (RU) was operated in parallel. In the last experimental phase, two sidestream anaerobic membrane bioreactors were evaluated: 1-AnMBR, which was fed with raw effluent; and, 2-AnMBR, which was fed with biologically acidified effluent. During the first operational phase, under an HRT of 3.3 h (OLR = 33 gCOD.L-1d-1), the FB, UG and UF-1 reactors showed continuous but unstable H2 production, with yields of approximately 1.5, 0.8 and 1.2 molH2.mol-1sucroseconsumed, respectively. The UF-1 reactor showed relatively better stability; therefore, this configuration was used in the next experiments. In the UF-2 reactor, the HRT was increased to 4.6 h (OLR = 25 gCOD.L-1d-1), which significantly improved the overall performance. No alkalizing agent was added, and effluent pH values remained around only 2.7. However, continuous, stable and long-term H2 production was achieved of 175 mLH2.L-1h-1 (= 4.2 LH2.L-1h-1), with yields of 3.4 molH2.mol-1sucroseconsumed, concomitant with acetic acid and ethanol production. In the methanogenic reactors, the HRT was gradually reduced and, when the systems reached stability, COD values remained lower in the RM effluent. This was mainly due to the reduction of VSS concentrations, equivalent to 92 mg.L-1, while in the RU this value was 244 mg.L-1. At the end of the operation, the energy yield of the two-stage system was 20.69 kJ.g-1CODadded with 90% coming from CH4 and 10% from H2. This yield was 34% greater than that obtained in the single-stage system, which was 15.48 kJ.g-1CODadded. Finally, regarding the filtration performance in the membrane bioreactors, the operational permeability was higher in the 2- AnMBR most of the time. The pre-acidification of the effluent led to the 56-59% reduction in the volatile total and suspended solid concentrations, and to modification in the particle size profile in the 2-AnMBR. Nevertheless, in the 1-AnMBR, there were no small particles such as were found in the sludge of the acidogenic reactor, indicating less suspended growth of acidogenic biomass. Although the critical flux values were very similar for both AnMBRs, a higher specific cake resistance was verified in the 1-AnMBR sludge (1.02 x 1018 m-1), as compared to the 2-AnMBR sludge (1.03 x 1012 m-1) and to the acidogenic sludge (7.44 x 1011m-1</sup). Therefore, this study demonstrated, through the application of two-stage anaerobic treatment, the viability of continuous hydrogen production in extreme acid pH and with minimum operating requirements, the reduction of solid concentrations in the effluent of structured fixed bed reactors, as well as the potential for increased bioenergy recovery and for fouling reduction of ultrafiltration membranes.

Le traitement des déchets alimentaires (FW) par digestion anaérobie peut conduire à une production d'énergie couplée à une réduction des émissions de volume et de gaz à effet de serre à partir de ce type de déchets. Néanmoins, l'obtention de la récupération du méthane la plus élevée possible dans un temps plus court avec un fonctionnement stable est difficile. Pour surmonter les obstacles de la MA de divers procédés de pré-traitement FW, la supplémentation en oligo-éléments, bioaugmentation utilisant la bouse des animaux de zoo et la comparaison des configurations de réacteurs, y compris une étape ou en deux réacteurs à cuve agités en continu (CSTR) et un réacteur à membrane anaérobie (AnMBR ) ont été étudiées dans le cadre de la présente recherche. Sur la base des résultats des expériences de traitement par lots, de pré-traitement thermique à 80 ° C pendant 1,5 heure cédés> 50% augmentation de la production de biométhane, et il a été trouvé à être plus économe en énergie que l'ozonation ou prétraitements de choc thermophiles. Parmi les différentes concentrations testées et les oligo-éléments, Fe (II) et Se (VI) des concentrations de 25 à 50 ug / L ont donné lieu à 39 et 35% d'augmentation de la production de biométhane, respectivement. Une meilleure solubilisation des protéines (6,96 ± 2,76% de plus) et de glucides récalcitrants (344,85 ± 54,31 mg / L par rapport à zéro) pourrait être obtenue avec bioaugmentation de girafe fumier (30% en volume), qui a donné un 11,24 ± 4,51% de plus production de biométhane. Un CSTR à deux étages avec digestat re-circulation de meilleurs résultats que d'un stade en raison de sa (i) une meilleure capacité d'auto-ajustement du pH; (ii) une plus grande résistance aux chocs de charge organique; (iii) de près de 100% de matières solides volatiles a été destryoed par rapport à 71% en CSTR une étape; (iv) 50 à 60% de teneur en méthane a été obtenu, alors qu'il était de 40 à 50% en une seule étape CSTR; (c) une petite quantité d'hydrogène a également été détectée à partir de la première étape du réacteur à deux étages qui en fait un système attrayant pour la production de biohythane. Bien que la séparation physique des méthanogènes rendus plus sensibles à des facteurs inhibiteurs, tels que l'ammonium et l'acide propionique. En outre, le temps de rétention hydraulique (HRT) est encore une chute de ces systèmes, d'où une AnMBR équipé d'une membrane de fluorure de vinylidène courant latéral a été proposé et exploité avec succès pour 100 d. Merci de membranes HRT a pu être réduite de 20 d à 1d, tout en conservant un rendement global d'élimination de> 97% de la demande en oxygène influent chimique (COD) et a abouti à une production de biogaz supérieure à 70% de teneur en méthane / Treatment of food waste by anaerobic digestion can lead to an energy production coupled to a reduction of the volume and greenhouse gas emissions from this waste type. Nevertheless, obtaining the highest possible methane recovery in a shorter time with a stable operation is challenging. To overcome the hurdles of AD of FW various pretreatment methods, supplementation of trace elements, bioaugmentation using zoo animals' dung and comparison of reactor configurations including one-stage and two-stage continuously stirred tank reactors (CSTR) as well as anaerobic membrane reactor (AnMBR) were studied in the scope of this research. Based on the results of the batch experiments, thermal pretreatment at 80°C for 1.5 hours yielded 46 – 52% higher biomethane production, and it is more energy efficient than ozonation or thermophilic shock pretreatments. Among the various tested concentrations and trace elements Fe (II) and Se (VI) concentrations of 25-50 ug/L resulted in 39 and 35% increase of biomethane production, respectively. A better solubilization of proteins (6.96 ± 2.76% more) and recalcitrant carbohydrates (344.85 ± 54.31 mg/L as compared to zero) could be obtained with bioaugmentation of giraffe dung (30% by volume), which yielded a 11.24 ± 4.51% higher biomethane production. A two-stage CSTR with digestate re-circulation performed better than one-stage with (i) a better pH self-adjusting capacity; (ii) a higher resistance to organic loading shocks; (iii) almost 100% volatile solids was destroyed as compared to 71% in one-stage CSTR; (iv) 50-60% methane content was obtained, while it was 40-50% in one-stage CSTR; (v) a small amount of hydrogen was also detected from the first stage of the two-stage reactor making it an attractive biohythane production system. Although physically separating the methanogens made them more sensitive to inhibitory factors, such as ammonium and propionic acid. Moreover, the long hydraulic retention time (HRT) is still the problem with these systems, hence an AnMBR equipped with a side-stream polyvinylidene fluoride membrane was proposed and a successful operation was achieved. Thanks to the membranes the HRT was able to be reduced from 20 d to 1d, while maintaining an overall removal efficiency of >97% of the influent chemical oxygen demand (COD) and yielded a higher biogas production with 70% methane content

The most significant environmental problems related to the food industry is water consumption and pollution, energy consumption and waste production. Most of the water that does not become a part of the products ultimately leaves plants in the form of wastewater, which is often very specific and requires adequate handling / treatment / disposal. For the purpose of this thesis, brewery industry was chosen, because of its very long tradition in the Czech history and culture. Anaerobic technologies are applied for still wider range of industrial wastewater treating. In general anaerobic membrane bioreactors (AnMBRs) can very effectively treat wastewater of different concentration and composition and produce treated water (outlet, permeate) of excellent quality, that can be further utilised. At the same time, it can promote energy self-sufficiency through biogas production usable in WWTPs / plants. Main disadvantages include unavoidable membrane fouling and generally higher CAPEX / OPEX. Within the framework of Ph.D. studies and related research activities, immersed membrane modules for anaerobic applications were selected and lab-scale tested (designed and assembled laboratory unit), an AnMBR pilot plant was designed, built and subsequently tested under real conditions - at Černá Hora Brewery WWTP (waste waters from the brewery and associated facilities). The pilot AnMBR and the technology itself has been verified over more than a year (5/2015 – 11/2016) of trial operation - the initial and recommended operational parameters have been set up, minor construction adjustments / modifications and measurement & regulation optimizations have been made, the recommended membrane cleaning and regeneration procedure has been verified. Last, but not least, conclusions and recommendations of the trial operation were summarised - some key findings and recommendations for further operation, use and modifications of the existing AnMBR pilot plant are presented.

El reactor anaerobio de membranas sumergidas (SAnMBR) está considerado como tecnología candidata para mejorar la sostenibilidad en el sector de la depuración de aguas residuales, ampliando la aplicabilidad de la biotecnología anaerobia al tratamiento de aguas residuales de baja carga (v.g. agua residual urbana) o a condiciones medioambientales extremas (v.g. bajas temperaturas de operación). Esta tecnología alternativa de tratamiento de aguas residuales es más sostenible que las tecnologías aerobias actuales ya que el agua residual se transforma en una fuente renovable de energía y nutrientes, proporcionando además un recurso de agua reutilizable. SAnMBR no sólo presenta las principales ventajas de los reactores de membranas (i.e. efluente de alta calidad, y pocas necesidades de espacio), sino que también presenta las principales ventajas de los procesos anaerobios. En este sentido, la tecnología SAnMBR presenta una baja producción de fangos debido a la baja tasa de crecimiento de los microorganismos implicados en la degradación de la materia orgánica, presenta una baja demanda energética debido a la ausencia de aireación, y permite la generación de metano, el cual representa una fuente de energía renovable que mejora el balance energético neto del sistema. Cabe destacar el potencial de recuperación de nutrientes del agua residual bien cuando el efluente es destinado a irrigación directamente, o bien cuando debe ser tratado previamente mediante tecnologías de recuperación de nutrientes. El objetivo principal de esta tesis doctoral es evaluar la viabilidad de la tecnología SAnMBR como núcleo en el tratamiento de aguas residuales urbanas a temperatura ambiente. Por lo tanto, esta tesis se centra en las siguientes tareas: (1) implementación, calibración y puesta en marcha del sistema de instrumentación, control y automatización requerido; (2) identificación de los parámetros de operación clave que afectan al proceso de filtración; (3) modelación y simulación del proceso de filtración; y (4) desarrollo de estrategias de control para la optimización del proceso de filtración minimizando los costes de operación. En este trabajo de investigación se propone un sistema de instrumentación, control y automatización para SAnMBR, el cual fue esencial para alcanzar un comportamiento adecuado y estable del sistema frente a posibles perturbaciones. El comportamiento de las membranas fue comparable a sistemas MBR aerobios a escala industrial. Tras más de dos años de operación ininterrumpida, no se detectaron problemas significativos asociados al ensuciamiento irreversible de las membranas, incluso operando a elevadas concentraciones de sólidos en el licor mezcla (valores de hasta 25 g·L-1 ). En este trabajo se presenta un modelo de filtración (basado en el modelo de resistencias en serie) que permitió simular de forma adecuada el proceso de filtración. Por otra parte, se propone un control supervisor basado en un sistema experto que consiguió reducir el consumo energético asociado a la limpieza física de las membranas, un bajo porcentaje de tiempo destinado a la limpieza física respecto al total de operación, y, en general, un menor coste operacional del proceso de filtración. Esta tesis doctoral está integrada en un proyecto nacional de investigación, subvencionado por el Ministerio de Ciencia e Innovación (MICINN), con título ¿Modelación de la aplicación de la tecnología de membranas para la valorización energética de la materia orgánica del agua residual y la minimización de los fangos producidos¿ (MICINN, proyecto CTM2008-06809- C02-01/02). Para obtener resultados representativos que puedan ser extrapolados a plantas reales, esta tesis doctoral se ha llevado a cabo utilizando un sistema SAnMBR que incorpora módulos comerciales de membrana de fibra hueca. Además, esta planta es alimentada con el efluente del pre-tratamiento de la EDAR del Barranco del Carraixet (Valencia, España). / Robles Martínez, Á. (2013). Modelling, simulation and control of the filtration process in a submerged anaerobic membrane bioreactor treating urban wastewater [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/34102 / Premios Extraordinarios de tesis doctorales