Företag har länge strävat efter att maximera kundnytta och bygga konkurrenskraft. Ett populärt sätt att göra det på är att använda sig av effektivitetsförbättrande filosofier. Lean Production är en sådan filosofi och den syftar till ett systematiskt förbättringsarbete i tillverkande företag där målet är att identifiera och eliminera slöserier för att bygga en snabbare och mer kvalitativ verksamhet. Det senaste decenniet har en utveckling av Lean Production ägt rum och återfinns nu även i en annan kontext, lagerverksamheter. På grund av e-handelns tillväxt har lagerverksamheter sett ett större behov av att ständigt arbeta med förbättringar och effektivisering. Eftersom Lean Production traditionellt varit anpassad till tillverkande företag har en specifik filosofi kallad Lean Warehousing utvecklats. Inom Lean Production har det arbetats fram vissa verktyg som syftar till att identifiera och eliminera slöserier i tillverkande företag. Dessa verktyg har inte anpassats till Lean Warehousing. Ett sådant verktyg är Value Stream Mapping, som syftar till att visualisera och kartlägga ett företags värdeskapande flöde med målet att identifiera slöserier. Tidigare forskning har visat att Value Stream Mapping har använts i en rad andra kontexter, däremot har ingen studie anpassat verktyget för lagerverksamheter. Detta har lett till studiens forskningsfråga: Hur kan Value Stream Mapping utvecklas för att bättre anpassas till en lagerverksamhet? Den teoretiska referensramen bygger på forskning inom området. Studier och litteratur om Lean Warehousing, lagerverksamheter i stort och om huvudaktiviteten orderplock presenteras. Kapitlet beskriver Value Stream Mapping och hur det använts i tillverkande företag. Vidare har det gjorts en genomgång av tidigare utvecklingar av verktyget och kapitlet avslutas sedan med att introducera ett nytt tillvägagångssätt. Avslutningsvis presenteras studiens resultat. De genomförda kvalitativa intervjuerna med hjälp av den teoretiska referensramen har utmynnat i en utvecklad modell – Warehouse Value Stream Mapping – med kontextspecifika anpassningar i form av mål kopplade till verksamheten och Key Performance Indicators som återspeglar orderplocket i lagerverksamheter. Föreliggande studie synliggör hur en anpassad modell av Value Stream Mapping bör se ut för att bättre kunna användas i lagerverksamheter i syfte att identifiera och eliminera slöseri och därmed effektivisera verksamheten.

Le veau nouveau-né possède un rumen peu développé et non fonctionnel. Au cours des premiers mois, les fonctions digestives s’établissent, avec l’implantation du microbiote composé majoritairement de bactéries, archées et protozoaires. Les objectifs de ce travail étaient doubles : i) caractériser et comprendre la séquence d’implantation taxonomique des microorganismes du rumen chez le veau par des techniques de biologie moléculaire et de dénombrement, ainsi que la séquence de mise en place des paramètres fermentaires (AGV et ammoniac) et des activités principales enzymatiques chez le veau en périodes pré- et post-sevrage, ii) étudier l’effet de l’addition de levures vivantes sur la mise en place de cet écosystème ruminal en périodes pré- et post-sevrage. D’une part, nos travaux ont permis de confirmer qu’à la naissance, le rumen chez le veau, est dépourvu de micro-organismes, d’AGV, d’activité xylanasique et amylasique, avec un pH proche de la neutralité et un Eh fortement positif. La colonisation du rumen se fait dès la naissance, pendant les 15 premiers jours de la vie de l’animal par un microbiote complexe prédominé par les bactéries (phyla Proteobacteria et Bacteroidetes) et comprenant aussi des archées (majoritairement Methanobrevibacter). En même temps, le Eh devient fortement négatif. Ces communautés entraînent la production de produits fermentaires grâce à leurs activités enzymatiques. Entre 15 jours et le sevrage, avec l’ingestion d’aliments solides, la composition du microbiote du rumen évolue pour se rapprocher de celle de ruminants adultes, sans atteindre pour autant la maturité en termes de densités et abondances relatives. A cette période, le phylum Bacteroidetes est majoritaire, avec le genre Prevotella. Après le sevrage de légers changements apparaissent sur certains paramètres fermentaires comme les AGV sans doute en raison d’une évolution du microbiote qui devient moins diversifié et plus adapté à la dégradation d’aliments solides. L’apparition, à partir de 90 jours, des protozoaires ciliés dans le rumen semble conditionnée par la présence d’animaux adultes à proximité. A 4 mois d’âge, l’écosystème ruminal tend à devenir proche de celui observé chez les animaux adultes en matière de paramètres fermentaires, activités enzymatiques et composition taxonomique du microbiote. D’autre part, nos travaux ont permis de conclure que, avant sevrage, une supplémentation en levures vivantes (Saccharomyces cerevisiae) diminue l’ingestion de concentrés, conduit à une apparition plus précoce de la communauté des protozoaires et une plus grande densité d’archées, mais a peu d'effets sur la densité et la diversité de la communauté bactérienne, à l'exception de variations d’abondances de quelques taxa mineurs. L’apport de levures entraîne une diminution de la protéolyse, une augmentation de la proportion d'acétate ruminal et une diminution de la proportion de propionate. Au cours de la période post-sevrage, les veaux supplémentés en levures consomment plus de foin et la densité en archées est plus importante alors qu’une réduction de la diversité et de la densité de la communauté bactérienne est observée, mais accompagnée d’une augmentation de l’abondance relative des bactéries dégradant l’amidon, les pectines, les protéines et majoritairement les parois cellulaires en fonction des substrats présents dans le rumen. Ces changements sont probablement à relier aux augmentations de l'activité xylanasique et de la proportion d'acétate. L’ensemble des résultats acquis dans ce travail de thèse a permis d’apporter un certain nombre de connaissances et une meilleure compréhension de la mise en place de l’écosystème ruminal chez le veau de race laitière en périodes pré- et post-sevrage, ainsi que quelques pistes pour orienter ou améliorer cette implantation pour une meilleure maîtrise de l’élevage des veaux d’élevage. / The newborn calf has a little and non-fonctional rumen. During the first months of life, digestive functions establish, in relationship with the colonization by a microbiota mainly composed of bacteria, archaea and protozoa. This study had two objectves: i) characterize and understand the sequence of establishment of ruminal microbiota in calves by molecular biology and counting techniques abd describe the appearance of fermentation parameters (VFA and ammonia) and enzyme activities during the pre- and post-weaning periods, ii) define the effect of yeast supplementation on the establishment of the ruminal ecosystem in pre-and post-weaning periods. On the one hand, our work confirmed that at birth, calf rumen is devoid of micro-organisms, AGV, xylanase and amylase activities, with a pH close to neutrality and a strongly positive Eh. From 2 to 15 days of age, the rumen is colonized by a complex microbiota dominated by bacteria (Proteobacteria and Bacteroidetes phyla) and also containing archaea (with mainly the Methanobrevibacter genus), and Eh becomes strongly negative. These communities result in the production of fermentation products due to their enzymatic activities. Between 15 days and weaning, with the ingestion of solid food, the composition of rumen microbiota changes to become closer to that of adult ruminants without reaching maturity in term of densities and relative abundances. At this time, the phylum Bacteroidetes is predominant with the Prevotella genus. After weaning, slight differences occurs on some fermentative parameters such as VFA, probably related to a change in the microbiota that becomes less diversified and more adapted to the degradation of solid food. From 90 days, the establishment of ciliated protozoa in the calf rumen seems conditioned by the proximity with adult animals. From 4 months of age, considering fermentation, enzymatic and taxonomic composition of the microbiota, the ruminal ecosystem tends to be similar to that observed in adult animals. On the other hand, our work showed that during the pre-weaning period, the supplementation with live yeast (Saccharomyces cerevisiae) results in a lower concentrate intake, an earlier establishment of ciliated protozoa and a higher archaeal community density, but poorly affects the density and diversity of the bacterial community, with the exception of changes in abundances of some minors taxa. Yeast supplementation reduces proteolysis, increases the proportion of acetate and decreases that of propionate. During the post-weaning period, yeast supplemented calves consumed more hay, had a higher archaeal density, but a lower diversity and density of the bacterial community with an increased relative abundance of fiber, protein, starch, pectine degrading bacteria compared to control according to the substrates present in the rumen. These changes are probably related to increases of the xylanolytic activity and the proportion of acetate. Taken together, results obtained in his thesis have improved knowledge and understanding of the establishment of the ruminal ecosystem in the dairy calf in pre- and post-weaning periods, and carried some possibilities to orientate or improve the ruminal establishment for better control of calves rearing.

Submitted by JOSIANE SANTOS DE OLIVEIRA (josianeso) on 2018-01-31T12:54:08Z No. of bitstreams: 1 Nara Paula Schmeier_.pdf: 877010 bytes, checksum: f002cde3446d9c5552d9a747ff097801 (MD5) / Made available in DSpace on 2018-01-31T12:54:08Z (GMT). No. of bitstreams: 1 Nara Paula Schmeier_.pdf: 877010 bytes, checksum: f002cde3446d9c5552d9a747ff097801 (MD5) Previous issue date: 2017-11-20 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Petrobras - Petróleo Brasileiro S. A. / PROSUP - Programa de Suporte à Pós-Gradução de Instituições de Ensino Particulares / O processo de digestão anaeróbia tem sido empregado com destaque no tratamento de resíduos sólidos orgânicos, por tratar-se de uma alternativa para amenizar problemas ambientais e também por uma questão energética, visto que possibilita a produção de energia para auxiliar a suprir a alta demanda, em consequência do elevado crescimento populacional e industrial. No entanto, questões relativas a escalas de trabalho, formas de operação, carga orgânica e influência de parâmetros como AGV, alcalinidade e nitrogênio amoniacal (NA) perduram. Desta forma o presente trabalho objetivou avaliar a operação de biodigestor, ao longo de 340 dias, mediante variação de frequências de adição de RSO e cargas orgânicas volumétricas (COV) de 7,98, 7,80, 9,64, 3,28, 4,10 e 5,00 kg STV/m3.d., com média de ST: 339,6 mg/g e umidade: 64%, frente a produção de biogás e CH4. Ademais, também buscou avaliar a influência de parâmetros como AGV, alcalinidade e nitrogênio amoniacal sobre o processo de DA. O sistema experimental foi composto por um biodigestor de câmara única, com volume de 0,28 m³, alimentado com RSO do restaurante universitário e inoculo ambientado a digestão de RSO. O monitoramento do processo experimental foi realizado por meio de caracterização físico-química (pH, DQO, DBO, alcalinidade, AGV, ST, STF, STV, NT, NA, PT e COT) das frações sólidas e líquidas, além da quantificação do biogás (volume e percentual de CH4). O processo de digestão revelou que aplicações de COVs de 3,28, 4,10 e 5,00 kg STV/m3.d. possibilitaram maiores rendimentos de biogás e CH4, em relação a COVs de 7,98, 7,80 e 9,64 kg STV/m3.d. A aplicação continua da COV de 4,10 kg STV/m3.d. apresentou o maior rendimento de biogás e CH4 em função dos STV aplicados, sendo 94,63 NL/kg STV e 45,42 NL/kg STV, respectivamente. No decorrer do processo de digestão, elevadas razões de AGV/Alcalinidade, baixas razões de C/NT e elevadas concentrações de AGV e NA levaram a uma condição de digestão que representou rendimentos reduzidos de biogás e metano. / The anaerobic digestion (AD) process has been used in the treatment of organic solid waste, for being an alternative to ease environmental problems and also an energy issue, since it allows the production of energy to help supplying the high demand, as a result of high population and industrial growth. However, issues concerning work scales, operation forms, organic loads and influence of parameters such as VFA, alkalinity and ammonia nitrogen (AN) to linger. In this way, the objective of this work was to evaluate the biodigester operation, during 340 days, by varying the frequencies of organic solid waste (OSW) and organic loading rate (OLR), of 7,98, 7,80, 9,64, 3,28, 4,10 e 5,00 kg STV/m3.d., with mean de TS: 339,6 mg/g and humidity: 64%, against production of biogas and CH4. In addition, it also sought to evaluate the influence of parameters such as VFA, alkalinity and AN on the DA process. The experimental system consisted of a single chamber biodigester with a volume of 0.28 m³, fed with OSW from a university restaurant and inoculum set to the digestion of OSW. The monitoring of the experimental process was carried out through physicochemical characterization (pH, COD, BOD, alkalinity, VFA, TS, TFS, TVS, TN, AN, PT and TOC) solid and liquid fractions, in addition to the quantification of biogas (volume and percentage of CH4). The digestion process revealed that OLRs applications of 3,28, 4,10 e 5,00 kg TVS/m3.d. allowed higher yields of biogas and CH4, in relation to OLRs of 7,98, 7,80 e 9,64 kg TVS/m3.d. The continuous application of OLR of 4,10 kg TVS/m3.d. showed the highest biogas yield and CH4 as a function of the VTS applied, being 94,63 NL/kg TVS and 45,42 NL/kg TVS, respectively. During the digestion process, high AGV/Alkalinity ratios, low C/N ratios and high concentrations of VFA and AN led to an digestion condition which represented reduced yields of biogas and methane.

O presente trabalho teve como objetivo principal avaliar a performance e a estabilidade operacional de uma nova configuração de um reator anaeróbio híbrido (RAH) que combina um filtro anaeróbio de fluxo descendente seguido de uma câmara de manta de lodo de fluxo ascendente comparativamente ao reator UASB nas mesmas condições operacionais aplicados ao tratamento de esgoto sanitário. A avaliação da eficiência de remoção de remoção da matéria orgânica e dos sólidos suspensos nos reatores piloto foi por meio de testes da DQO, DBO, sólidos em suspensão totais (SST) e dos sólidos em suspensão voláteis (SSV).Os reatores UASB e RAH foram operados por um período de 240 dias na fase 1 e 150 dias na fase 2 com vazão afluente de 1,6 m3/h e TDH de 11,8 h. O TDH médio na câmara de entrada do RAH foi de 2,7h e de 9,1h na câmara ascendente de manto de lodo. Os reatores piloto apresentaram capacidade de tratamento para suportar os choques de carga orgânica devido à variabilidade do esgoto bruto. A eficiência de remoção de matéria orgânica em termos de DQO foi de 66% e 59% para o UASB e RAH, a eficiência de remoção de SST atingiu valores de 65% e 63% respectivamente, aliás, o reator UASB apresentando valores superiores de desempenho operacional em quase todos os parâmetros de monitoramento dos processos de digestão anaeróbia os valores médios dos parâmetros DQO, DBO5, SST e SSV não tiveram diferenças estatisticamente significativas. O pH para os sistemas piloto esteve na faixa ideal para o desenvolvimento dos microorganismos anaeróbios (6,5 a 7,5) e a alcalinidade e os AGVs demonstraram estabilidade dos reatores, corroborados pela estabilidade do pH no interior de cada sistema. A velocidade ascensional na câmara de manta de lodo (0,45 m/h) não causou efeito adverso na qualidade do efluente em termos de SST, com valor médio de 39,8 mg/L, na mesma faixa observada no reator UASB (41,6 mg/L). Foi observada menor concentração de biomassa no reator RAH (distribuição vertical) comparativamente ao reator UASB segundo os perfis verticais de lodo, entretanto, este fato não comprometeu a sua eficiência de remoção de matéria orgânica e dos sólidos suspensos. A retirada do lodo de excesso dos sistemas piloto foi baseada na relação STV/ST para estimar a fração de biomassa, a freqüência do descarte foi de 1 vez por mês retirando o equivalente aos 10% do volume de lodo das tomadas que apresentaram uma fração de STV menor que 50%. É viável a implementação da turbidez como parâmetro de detenção de perdida de lodo no efluente dos reatores anaeróbios devido a que a turbidez e os SST apresentaram uma relação direta o que ajudaria a simplificar mecanismos de controle operacional para a toma de decisões nas estações de tratamento, sendo que a turbidez é um parâmetro de leitura rápida “in situ” e poderia advertir do excesso de lodo ao interior do reator. Foram empregados diferentes métodos titrimétricos para a determinação dos AGVs no efluente do RAH e UASB. Após análise dos resultados, recomenda-se o uso do método de KAPP e RIPLEY para a determinação dos AGVs pela simplicidade metodológica e pela rapidez na obtenção do resultado. / This study aimed to evaluate the performance and operational stability of a new configuration of a hybrid anaerobic reactor (RAH) combining an anaerobic filter downflow followed by a sludge blanket chamber upflow compared to UASB in same operating conditions applied to sewage treatment. The evaluation of organic matter removal and removal efficiency of suspended solids in the pilot reactor was by testing COD, BOD, total suspended solids (TSS) and volatile suspended solids (VSS). The RAH and UASB reactors were operated for a period of 240 days in the first phase and 150 days in phase 2 with the inlet flow of 1,6 m3/h and 11,8h TDH. The average TDH RAH in the inlet chamber was 2.7h and 9,1h in ascending chamber sludge blanket. Pilot reactors showed treatment capacity to support organic shock loads due to the variability of raw sewage. The organic matter removal efficiency in terms of COD was 66% and 59% for the UASB and RAH, the TSS removal efficiency reached values of 65% and 63% respectively, by the way, the UASB presenting performance values higher operational in almost all parameters of the monitoring anaerobic digestion processes mean values of the parameters COD, BOD5, TSS and VSS were not statistically significant differences. The pH for the pilot systems was in the ideal range for the development of anaerobic microorganisms (6,5 to 7,5) and alkalinity and Volatile Fatty Acids (VFA) demonstrated stability of reactors corroborated by the pH stability within each system. The upflow velocity in the sludge blanket chamber (0,45 m/h) caused no adverse effect on effluent quality in terms of TSS, with an average of 39,8 mg/L, in the same range observed in UASB (41,6 mg/L). It was observed lower concentration of biomass in the reactor RAH (vertical distribution) compared to UASB second vertical sludge profiles, however, this fact did not compromise its removal efficiency of organic matter and suspended solids. The withdrawal of the pilot systems excess sludge was based on TSV/TS ratio to estimate the biomass fraction, the frequency of disposal was 1 once a month by removing the equivalent of 10% of the outlets sludge volume that had a fraction of TSV less than 50%. The implementation of turbidity as sludge lost detention parameter is viable in the effluent of the anaerobic reactors due to turbidity and TSS showed a direct relationship which would help simplify operational control mechanisms for decision making in treatment plants, wherein the turbidity is a quick read parameter "in situ" and could warn of excess sludge inside the reactor. Different titrimetric methods were employed for the determination of VFA and the effluent from the UASB and RAH. After analyzing the results, we recommend the use of KAPP and RIPLEY method for the determination of VFA by methodological simplicity and speed in obtaining results.

Polyhydroxyalkanoates (PHA) are a family of biodegradable polyesters naturally synthesised by some bacteria and archaea. PHA have high industrial value as bioplastics for packaging and biomedical applications. However, their broader use is hindered by high production costs and uncontrolled variation of polymer properties. The extreme halophile Haloferax mediterranei shows bioprocess advantages that can be exploited for the low cost production of the PHA copolymer Poly(3-hydroxbutyrate-co-3-hydroxyvalterate) (PHBV). The focus of this thesis is to identify process variables responsible for the uncontrolled variation of PHA properties in order to progress towards the robust production of PHBV using H. mediterranei. The outcome of the investigation is a novel cultivation strategy for the reliable synthesis of PHBV copolymers with controlled composition and microstructure showing minor differences in material characteristics. Initially, growth kinetics and PHBV synthesis were characterised under nitrogen-excess and nitrogen-limiting conditions in ammonium and for the first time, nitrate. The nitrogen source and concentration influenced PHBV accumulation and variations in polymer composition were observed with ammonium, highlighting the importance of the control of cultivation conditions. Volatile fatty acids (VFA) were found to be a more direct approach to determine PHBV composition and for the first time were used as substrates in H. mediterranei cultures. When the cells were grown in C4:0/C5:0 mixtures, the 3HV fraction in the PHBV was proportional to the percentage of C5:0 in the feed mixture, allowing the synthesis of copolymers with a predefined composition ranging from pure PHB to pure PHV. The cultivation strategy proved effective for the synthesis of HV rich PHBV, which is not easily obtained due to the 3HV precursor toxicity. The polymer microstructure was controlled using different feeding strategies: co-feeding generated random copolymers, while sequential feeding created block and blend copolymers. The synthesis of block copolymers is of interest because the materials show enhanced yield strength and mechanical strength, making such materials more suitable for commodity uses. Bespoke random, block, and blend copolymers with 0−100 mol% 3HV were synthesized and their thermal and mechanical properties studied. Lastly, high temperature cultivation and several surfactants were tested to enhance the production of bespoke PHBV from VFA. PHBV productivity and accumulation was greatly improved in a fed-batch bioreactor fermentation at 37°C with Tween-80 and the maximum PHBV content 58.9% was obtained. The polymers from shake-flasks and from bioreactors showed minor variations in their material properties, demonstrating the scalability and the robustness of the process developed. Further understanding of the different process variables affecting polymer synthesis and composition was gained in this thesis. It is now possible to produce PHBV with controllable composition, microstructure and minor differences in material characteristics. The novel and robust production strategy developed address the bioprocess challenge of minimising the uncontrolled variation of polymer characteristics that is currently hindering the wider use of PHA hence allowing the production of high quality polymers for commodity goods, packaging and biomedical applications.

The objective of this study is to illustrate that phase separation improves the efficiency of an anaerobic system which digests semi-solid organic wastes. Organic fraction of municipal solid waste (OFMSW) was the semi-solid organic waste investigated. In the first part of the study, the optimum operational conditions for acidified reactor were determined by considering the volatile solid (VS) reductions and average acidification percentages at the end of two experimental sets conducted. Organic loading rate (OLR) of 15 g VS/L.day, pH value of 5.5 and hydraulic retention time (HRT) of 2 days were determined to be the optimum operational conditions for the acidification step. Maximum total volatile fatty acid and average acidification percentage were determined as 12405 mg as HAc/L and 28%, respectively in the reactor operated at optimum conditions. In the second part, an acidification reactor was operated at the optimum conditions determined in the first part. The effluents taken from this reactor as well as the waste stock used to feed this reactor were used as substrate in the biochemical methane potential (BMP) test. The results of BMP test revealed that the reactors fed by acidified samples indicated higher total chemical oxygen demand (tCOD) removals (39%), VS reductions (67%) and cumulative gas productions (265 mL). The result of this study indicated that the separation of the reactors could lead efficiency enhancement in the systems providing that effective control was achieved on acidified reactors.

O presente trabalho teve como objetivo principal avaliar a performance e a estabilidade operacional de uma nova configuração de um reator anaeróbio híbrido (RAH) que combina um filtro anaeróbio de fluxo descendente seguido de uma câmara de manta de lodo de fluxo ascendente comparativamente ao reator UASB nas mesmas condições operacionais aplicados ao tratamento de esgoto sanitário. A avaliação da eficiência de remoção de remoção da matéria orgânica e dos sólidos suspensos nos reatores piloto foi por meio de testes da DQO, DBO, sólidos em suspensão totais (SST) e dos sólidos em suspensão voláteis (SSV).Os reatores UASB e RAH foram operados por um período de 240 dias na fase 1 e 150 dias na fase 2 com vazão afluente de 1,6 m3/h e TDH de 11,8 h. O TDH médio na câmara de entrada do RAH foi de 2,7h e de 9,1h na câmara ascendente de manto de lodo. Os reatores piloto apresentaram capacidade de tratamento para suportar os choques de carga orgânica devido à variabilidade do esgoto bruto. A eficiência de remoção de matéria orgânica em termos de DQO foi de 66% e 59% para o UASB e RAH, a eficiência de remoção de SST atingiu valores de 65% e 63% respectivamente, aliás, o reator UASB apresentando valores superiores de desempenho operacional em quase todos os parâmetros de monitoramento dos processos de digestão anaeróbia os valores médios dos parâmetros DQO, DBO5, SST e SSV não tiveram diferenças estatisticamente significativas. O pH para os sistemas piloto esteve na faixa ideal para o desenvolvimento dos microorganismos anaeróbios (6,5 a 7,5) e a alcalinidade e os AGVs demonstraram estabilidade dos reatores, corroborados pela estabilidade do pH no interior de cada sistema. A velocidade ascensional na câmara de manta de lodo (0,45 m/h) não causou efeito adverso na qualidade do efluente em termos de SST, com valor médio de 39,8 mg/L, na mesma faixa observada no reator UASB (41,6 mg/L). Foi observada menor concentração de biomassa no reator RAH (distribuição vertical) comparativamente ao reator UASB segundo os perfis verticais de lodo, entretanto, este fato não comprometeu a sua eficiência de remoção de matéria orgânica e dos sólidos suspensos. A retirada do lodo de excesso dos sistemas piloto foi baseada na relação STV/ST para estimar a fração de biomassa, a freqüência do descarte foi de 1 vez por mês retirando o equivalente aos 10% do volume de lodo das tomadas que apresentaram uma fração de STV menor que 50%. É viável a implementação da turbidez como parâmetro de detenção de perdida de lodo no efluente dos reatores anaeróbios devido a que a turbidez e os SST apresentaram uma relação direta o que ajudaria a simplificar mecanismos de controle operacional para a toma de decisões nas estações de tratamento, sendo que a turbidez é um parâmetro de leitura rápida “in situ” e poderia advertir do excesso de lodo ao interior do reator. Foram empregados diferentes métodos titrimétricos para a determinação dos AGVs no efluente do RAH e UASB. Após análise dos resultados, recomenda-se o uso do método de KAPP e RIPLEY para a determinação dos AGVs pela simplicidade metodológica e pela rapidez na obtenção do resultado. / This study aimed to evaluate the performance and operational stability of a new configuration of a hybrid anaerobic reactor (RAH) combining an anaerobic filter downflow followed by a sludge blanket chamber upflow compared to UASB in same operating conditions applied to sewage treatment. The evaluation of organic matter removal and removal efficiency of suspended solids in the pilot reactor was by testing COD, BOD, total suspended solids (TSS) and volatile suspended solids (VSS). The RAH and UASB reactors were operated for a period of 240 days in the first phase and 150 days in phase 2 with the inlet flow of 1,6 m3/h and 11,8h TDH. The average TDH RAH in the inlet chamber was 2.7h and 9,1h in ascending chamber sludge blanket. Pilot reactors showed treatment capacity to support organic shock loads due to the variability of raw sewage. The organic matter removal efficiency in terms of COD was 66% and 59% for the UASB and RAH, the TSS removal efficiency reached values of 65% and 63% respectively, by the way, the UASB presenting performance values higher operational in almost all parameters of the monitoring anaerobic digestion processes mean values of the parameters COD, BOD5, TSS and VSS were not statistically significant differences. The pH for the pilot systems was in the ideal range for the development of anaerobic microorganisms (6,5 to 7,5) and alkalinity and Volatile Fatty Acids (VFA) demonstrated stability of reactors corroborated by the pH stability within each system. The upflow velocity in the sludge blanket chamber (0,45 m/h) caused no adverse effect on effluent quality in terms of TSS, with an average of 39,8 mg/L, in the same range observed in UASB (41,6 mg/L). It was observed lower concentration of biomass in the reactor RAH (vertical distribution) compared to UASB second vertical sludge profiles, however, this fact did not compromise its removal efficiency of organic matter and suspended solids. The withdrawal of the pilot systems excess sludge was based on TSV/TS ratio to estimate the biomass fraction, the frequency of disposal was 1 once a month by removing the equivalent of 10% of the outlets sludge volume that had a fraction of TSV less than 50%. The implementation of turbidity as sludge lost detention parameter is viable in the effluent of the anaerobic reactors due to turbidity and TSS showed a direct relationship which would help simplify operational control mechanisms for decision making in treatment plants, wherein the turbidity is a quick read parameter "in situ" and could warn of excess sludge inside the reactor. Different titrimetric methods were employed for the determination of VFA and the effluent from the UASB and RAH. After analyzing the results, we recommend the use of KAPP and RIPLEY method for the determination of VFA by methodological simplicity and speed in obtaining results.

O presente trabalho teve como objetivo principal avaliar a performance e a estabilidade operacional de uma nova configuração de um reator anaeróbio híbrido (RAH) que combina um filtro anaeróbio de fluxo descendente seguido de uma câmara de manta de lodo de fluxo ascendente comparativamente ao reator UASB nas mesmas condições operacionais aplicados ao tratamento de esgoto sanitário. A avaliação da eficiência de remoção de remoção da matéria orgânica e dos sólidos suspensos nos reatores piloto foi por meio de testes da DQO, DBO, sólidos em suspensão totais (SST) e dos sólidos em suspensão voláteis (SSV).Os reatores UASB e RAH foram operados por um período de 240 dias na fase 1 e 150 dias na fase 2 com vazão afluente de 1,6 m3/h e TDH de 11,8 h. O TDH médio na câmara de entrada do RAH foi de 2,7h e de 9,1h na câmara ascendente de manto de lodo. Os reatores piloto apresentaram capacidade de tratamento para suportar os choques de carga orgânica devido à variabilidade do esgoto bruto. A eficiência de remoção de matéria orgânica em termos de DQO foi de 66% e 59% para o UASB e RAH, a eficiência de remoção de SST atingiu valores de 65% e 63% respectivamente, aliás, o reator UASB apresentando valores superiores de desempenho operacional em quase todos os parâmetros de monitoramento dos processos de digestão anaeróbia os valores médios dos parâmetros DQO, DBO5, SST e SSV não tiveram diferenças estatisticamente significativas. O pH para os sistemas piloto esteve na faixa ideal para o desenvolvimento dos microorganismos anaeróbios (6,5 a 7,5) e a alcalinidade e os AGVs demonstraram estabilidade dos reatores, corroborados pela estabilidade do pH no interior de cada sistema. A velocidade ascensional na câmara de manta de lodo (0,45 m/h) não causou efeito adverso na qualidade do efluente em termos de SST, com valor médio de 39,8 mg/L, na mesma faixa observada no reator UASB (41,6 mg/L). Foi observada menor concentração de biomassa no reator RAH (distribuição vertical) comparativamente ao reator UASB segundo os perfis verticais de lodo, entretanto, este fato não comprometeu a sua eficiência de remoção de matéria orgânica e dos sólidos suspensos. A retirada do lodo de excesso dos sistemas piloto foi baseada na relação STV/ST para estimar a fração de biomassa, a freqüência do descarte foi de 1 vez por mês retirando o equivalente aos 10% do volume de lodo das tomadas que apresentaram uma fração de STV menor que 50%. É viável a implementação da turbidez como parâmetro de detenção de perdida de lodo no efluente dos reatores anaeróbios devido a que a turbidez e os SST apresentaram uma relação direta o que ajudaria a simplificar mecanismos de controle operacional para a toma de decisões nas estações de tratamento, sendo que a turbidez é um parâmetro de leitura rápida “in situ” e poderia advertir do excesso de lodo ao interior do reator. Foram empregados diferentes métodos titrimétricos para a determinação dos AGVs no efluente do RAH e UASB. Após análise dos resultados, recomenda-se o uso do método de KAPP e RIPLEY para a determinação dos AGVs pela simplicidade metodológica e pela rapidez na obtenção do resultado. / This study aimed to evaluate the performance and operational stability of a new configuration of a hybrid anaerobic reactor (RAH) combining an anaerobic filter downflow followed by a sludge blanket chamber upflow compared to UASB in same operating conditions applied to sewage treatment. The evaluation of organic matter removal and removal efficiency of suspended solids in the pilot reactor was by testing COD, BOD, total suspended solids (TSS) and volatile suspended solids (VSS). The RAH and UASB reactors were operated for a period of 240 days in the first phase and 150 days in phase 2 with the inlet flow of 1,6 m3/h and 11,8h TDH. The average TDH RAH in the inlet chamber was 2.7h and 9,1h in ascending chamber sludge blanket. Pilot reactors showed treatment capacity to support organic shock loads due to the variability of raw sewage. The organic matter removal efficiency in terms of COD was 66% and 59% for the UASB and RAH, the TSS removal efficiency reached values of 65% and 63% respectively, by the way, the UASB presenting performance values higher operational in almost all parameters of the monitoring anaerobic digestion processes mean values of the parameters COD, BOD5, TSS and VSS were not statistically significant differences. The pH for the pilot systems was in the ideal range for the development of anaerobic microorganisms (6,5 to 7,5) and alkalinity and Volatile Fatty Acids (VFA) demonstrated stability of reactors corroborated by the pH stability within each system. The upflow velocity in the sludge blanket chamber (0,45 m/h) caused no adverse effect on effluent quality in terms of TSS, with an average of 39,8 mg/L, in the same range observed in UASB (41,6 mg/L). It was observed lower concentration of biomass in the reactor RAH (vertical distribution) compared to UASB second vertical sludge profiles, however, this fact did not compromise its removal efficiency of organic matter and suspended solids. The withdrawal of the pilot systems excess sludge was based on TSV/TS ratio to estimate the biomass fraction, the frequency of disposal was 1 once a month by removing the equivalent of 10% of the outlets sludge volume that had a fraction of TSV less than 50%. The implementation of turbidity as sludge lost detention parameter is viable in the effluent of the anaerobic reactors due to turbidity and TSS showed a direct relationship which would help simplify operational control mechanisms for decision making in treatment plants, wherein the turbidity is a quick read parameter "in situ" and could warn of excess sludge inside the reactor. Different titrimetric methods were employed for the determination of VFA and the effluent from the UASB and RAH. After analyzing the results, we recommend the use of KAPP and RIPLEY method for the determination of VFA by methodological simplicity and speed in obtaining results.

Ce travail de thèse a eu pour objectif principal l'étude thermodynamique des changements métaboliques dans l'acidogénèse. L'acidogénèse est un procédé anaérobie à double intérêt qui en traitant des résidus organiques, permet de produire des composés chimiques comme l'hydrogène, l'éthanol et les acides organiques. Par conséquent, l'acidogénèse se place comme un procédé biotechnologique dans le concept de bioraffinerie. En outre, ce processus n'a pas besoin de conditions stériles d'opération et fonctionne sur une large gamme de pH. Ces changements métaboliques sont dépendants des modifications dans les conditions opératoires. Afin d'étudier ces changements métaboliques, des expériences basées sur des modifications du ciel gazeux du réacteur par introduction d'azote et sur des changements du pH, ont été menées. Un des résultats les plus intéressants a été l'augmentation du rendement de production d'hydrogène de 1 à 3,2 molH2/molglucose à pH 4,5 et débit de N2 de 58,4 L/d. Ce rendement est proche de la valeur théorique (4 molH2/molglucose). L'étude thermodynamique a permis d'expliquer les mécanismes métaboliques concernant l'hydrogène, dont la production importante, représentée par le rendement de 3,2 molH2/molglucose, est due à la réaction inverse H2/NAD+, qui est thermodynamiquement faisable à faibles pressions partielles d'hydrogène (par exemple 0,02 bar). En outre, les bas rendements en hydrogène ont été expliqués par l'action consommatrice d'hydrogène par la réaction d'homoacetogénèse. Cependant, le modèle n'a pas été capable d'expliquer les changements métaboliques de l'acétate, du butyrate et de l'éthanol lors de la fermentation acidogénique du glucose. / This thesis deals with thermodynamic based modelling of metabolic shifts during acidogenic fermentation. Acidogenic fermentation is an anaerobic process of double purpose: while treating organic residues, it produces chemical compounds, such as hydrogen, ethanol and organic acids. Therefore, acidogenic fermentation arises as an attractive biotechnology process towards the biorefinery concept. Moreover, this process does not need sterile operating conditions and works under a wide range of pH.Changes of operating conditions produce metabolic shifts, inducing variability on acidogenic product yields. In order to study these metabolic shifts, an experiment design was based on reactor headspace N2-flushing (gas phase) and pH step changes (liquid phase). A major result was the hydrogen yield increase from 1 to 3.2 (molH2/molglucose) at pH 4.5 and N2-flushing of 58.4 L/d. This yield is close to the theoretical acidogenic value (4 molH2/molglucose).The thermodynamic model, based on the assumption that acidogenic fermentation is characterised by limited energy available for biological process, allowed to explain the mechanisms that govern hydrogen metabolic shifts, showing that the synthesis of extra hydrogen, i.e. yield of 3.2 (molH2/molglucose), was due to reverse H2/NAD+ redox reaction, which is thermodynamically feasible at low hydrogen partial pressures (e.g. 0.02 bar). Moreover, low hydrogen yields were explained by the action of homoacetogenesis hydrogen consuming reaction. However, the model was not capable to explain the metabolic shifts of acetate, butyrate and ethanol on acidogenic glucose fermentation.

[EN] Phosphorus is very important in life because it plays an essential role in biological processes. The main use of phosphorus is in the fertilizer industry in the form of phosphates. These phosphates come mainly from phosphate rocks which might be exhausted in 50-100 years. The overexploitation of phosphate rocks has resulted in decreased quality of reserves, and it has raised the cost of extraction, processing and shipping. Moreover, phosphorus coming from wastewater, phosphate rock dissolution, and soil with an excessive supply of fertilizer, is deposited on the surface water bodies causing a serious pollution problem called eutrophication. One of the systems most used to reduced phosphorus levels in the wastewater is the enhanced biological phosphorus removal (EBPR). This process involves capturing biologically, alternating between anaerobic oxic/anoxic conditions, the wastewater phosphorus through the phosphorus accumulating organisms (PAOs). However, one of the main problems of this process is that the glycogen accumulating organisms (GAOs) compete with PAOs for volatile fatty acids (VFA). Even though there have been many studies on the factors affecting competition between PAOs and GAOs, there are still many unanswered questions regarding the metabolism of PAOs when they lack energy reserves in the form of intracellular polyphosphates (poly-P) and its effect on the population dynamics of PAOs and GAOs in an activated sludge system. Therefore, the main goal of this dissertation is to study short- and long-term the metabolic behavior of the PAOs to different levels of poly-P; to analyze the population dynamics of microorganisms involved in the process EBPR; to model mathematically that metabolic behavior; and finally, to evaluate the possible recovery of phosphorus by extracting poly-P present in the PAOs. In the short- and long-term study was observed a metabolic shift correlates with the content in poly-P so that under low contents of poly-P the PAOs are able to behave as GAOs but without a significant development of the GAO population. Although, in both studies was observed the same metabolic behavior, from the microbiological point of view were observed some differences. In the short-term, the PAO Type II clearly showed the metabolic shift, while long-term were the PAO Type I. From the experiments performed, necessary expressions (stoichiometric and kinetic) were developed to include new behaviors observed (metabolic rate) in metabolic models existing today. Monod type expressions were developed and implemented on the model of the PAOs to represent the change between the typical stoichiometric parameters of PAO and GAO metabolism. The model was calibrated and validated showing the ability to correctly represent the metabolic change of PAOs under low concentrations of poly-P. When was observed that with low concentrations of poly-P the PAOs have the ability to change its metabolism, without the process was deteriorated by the development of the GAO population, two operating strategies were evaluated to obtain a stream rich in phosphorus to allow later retrieval. The strategies studied differed in the level of extraction of the poly-P from PAOs. In the first strategy, it was extracted less than 40 % of poly-P, while the second strategy, it came to extract more than 90 % of poly-P. The second strategy showed a higher extraction efficiency, achieving recover up to 81 % of the phosphorus present in the wastewater. As a result, of work performed four articles were generated, three of them published in journals of particular importance (2 in the journal Water Research and 1 in the journal Chemical Engineering Journal) constituting the main body of this thesis. / [ES] El fósforo es de gran importancia para la vida debido a que desempeña un papel esencial en los procesos biológicos. El principal uso del fósforo está en la industria de los fertilizantes en forma de fosfatos. Estos fosfatos provienen principalmente de las rocas fosfáticas, las cuales podrían llegar a agotarse entre los próximos 50 y 100 años. La sobreexplotación de la roca fosfática, ha generado una disminución en la calidad de las reservas, y ha elevado el coste de su extracción, procesamiento y transporte marítimo. Por otra parte, el fósforo proveniente de las aguas residuales, de la disolución de las rocas fosfáticas y de los suelos con excesivo aporte de fertilizantes, se deposita en los cuerpos de aguas superficiales produciendo un grave problema de contaminación llamado eutrofización. Uno de los sistemas más empleados para reducir los niveles de fósforo en el agua residual es el proceso de eliminación biológica de fósforo (EBPR). Este proceso implica capturar biológicamente, alternando entre condiciones anaerobias óxicas/anóxicas, el fósforo del agua residual mediante organismos acumuladores de fósforo (PAOs). Sin embargo, uno de los principales problemas de este proceso, es la competencia de las PAOs con los organismos acumuladores de glucógeno (GAOs) por los ácidos grasos volátiles (AGV). Aunque si bien se han realizado muchos estudios sobre los factores que afectan la competencia entre PAOs y GAOs, existen aún muchas preguntas sin respuesta en relación al metabolismo de las PAOs cuando estas carecen de reservas energéticas en forma de polifosfatos intracelulares (poli-P) y a su efecto sobre la dinámica de las poblaciones de PAOs y GAOs en un sistema de fangos activados. Es por ello que el objetivo principal de esta tesis doctoral consiste en: estudiar a corto y largo plazo el comportamiento metabólico de las PAOs al cambiar el contenido en poli-P; analizar la dinámica poblacional de los microorganismos implicados en el proceso de EBPR; modelizar matemáticamente dicho comportamiento metabólico y por último evaluar la posible recuperación de fósforo mediante la extracción del poli-P presente en las PAOs. En el estudio a corto y largo plazo se observó un cambio metabólico correlacionado con el contenido en poli-P, de forma que a bajos contenidos de poli-P las PAOs se comportaban metabólicamente como las GAOs, pero sin que estas últimas se llegaran a desarrollar de forma significativa. A pesar de observar el mismo comportamiento metabólico en ambos estudios, desde el punto de vista microbiológico se observaron diferencias. A corto plazo, las PAO Tipo II mostraron claramente el cambio metabólico, mientras que a largo plazo fueron las PAO Tipo I. A partir de los experimentos realizados, se desarrollaron las expresiones necesarias (estequiométricas y cinéticas) para incluir los nuevos comportamientos observados (cambio metabólico) en los modelos metabólicos existentes en la actualidad. Expresiones tipo Monod fueron desarrolladas e implementadas en el modelo de las PAOs para representar el cambio entre los parámetros estequiométricos típicos del metabolismo PAO y GAO. El modelo fue calibrado y validado mostrando la capacidad de representar correctamente el cambio metabólico de las PAOs a concentraciones bajas de poli-P. Al observar que las PAOs tienen la habilidad de cambiar su metabolismo a bajas concentraciones de poli-P, sin que se deteriorara el proceso por el desarrollo de las GAOs, se evaluaron dos estrategias de operación para la obtención de una corriente rica en fósforo que permita su posterior recuperación. Las estrategias estudiadas se diferenciaban en el nivel de extracción de poli-P de las PAOs. En la primera estrategia se extraía menos del 40 % de poli-P, mientras que en la segunda estrategia se llegaba a extraer más del 90 % de poli-P. La segunda estrategia mostró una eficacia de extracción superior, consiguiendo recuperar hasta el 81 / [CAT] El fòsfor és de gran importància per a la vida a causa que exerceix un paper essencial en els processos biològics. El principal ús del fòsfor està en la indústria dels fertilitzants en forma de fosfats. Aquests fosfats provenen principalment de les roques fosfatades, les quals podrien arribar a esgotar-se entre els pròxims 50 i 100 anys. La sobreexplotació de la roca fosfatada, ha generat una disminució en la qualitat de les reserves, i ha elevat el cost de la seua extracció, processament i transport marítim. D'altra banda, el fòsfor provinent de les aigües residuals, de la dissolució de les roques fosfatades i dels sòls amb excessiva aportació de fertilitzants, es diposita en els cossos d'aigües superficials produint un greu problema de contaminació anomenat eutrofització. Un dels sistemes més utilizats per a reduir els nivells de fòsfor en l'aigua residual és el procés d'eliminació biològica de fòsfor (EBPR). Aquest procés implica capturar biològicament, alternant entre condicions anaeròbies aeròbies/anòxies, el fòsfor de l'aigua residual mitjançant organismes acumuladors de fòsfor (PAOs). No obstant açò, un dels principals problemes d'aquest procés, és la competència de les PAOs amb els organismes acumuladors de glucogen (GAOs) pels àcids grassos volàtils (AGV). Encara que si bé s'han realitzat molts estudis sobre els factors que afecten la competència entre PAOs i GAOs, existixen encara moltes preguntes sense resposta en relació al metabolisme de les PAOs quan aquestes careixen de reserves energètiques en forma de polifosfat intracel·lulars (poli-P) i al seu efecte sobre la dinàmica de les poblacions de PAOs i GAOs en un sistema de fangs activats. És per això que l'objectiu principal d'aquesta tesi doctoral consisteix en: estudiar a curt i llarg termini el comportament metabòlic de les PAOs en canviar el contingut en poli-P; analitzar la dinàmica poblacional dels microorganismes implicats en el procés de EBPR; modelatge matemàticament d'aquest comportament metabòlic i finalment avaluar la possible recuperació de fòsfor mitjançant l'extracció del poli-P present en les PAOs. En l'estudi a curt i llarg termini es va observar un canvi metabòlic correlacionat amb el contingut en poli-P, de manera que a baixos continguts de poli-P les PAOs es comportaven metabolicament com les GAOs, però sense que aquestes últimes s'arribaren a desenvolupar de forma significativa. Malgrat observar el mateix comportament metabòlic en tots dos estudis, des del punt de vista microbiològic es van observar diferències. A curt termini, les PAO Tipus II van mostrar clarament el canvi metabòlic, mentre que a llarg termini van ser les PAO Tipus I. A partir dels experiments realitzats, es van desenvolupar les expressions necessàries (estequiomètriques i cinètiques) per a incloure els nous comportaments observats (canvi metabòlic) en els models metabòlics existents en l'actualitat. Expressions tipus Monod van ser desenvolupades e implementades en el model de les PAOs per a representar el canvi entre els paràmetres estequiomètrics típics del metabolisme PAO i GAO. El model va ser calibrat i validat mostrant la capacitat de representar correctament el canvi metabòlic de les PAOs a concentracions baixes de poli-P. En observar que les PAOs tenen l'habilitat de canviar el seu metabolisme a baixes concentracions de poli-P, sense que es deteriorara el procés pel desenvolupament de les GAOs, es varen avaluar dues estratègies d'operació per a l'obtenció d'un corrent ric en fòsfor que permeta la seua posterior recuperació. Les estratègies estudiades es diferenciaven en el nivell d'extracció de poli-P de les PAOs. En la primera estratègia es va extraure menys del 40 % de poli-P, mentre que en la segona estratègia s'arribava a extraure més del 90 % de poli-P. La segona estratègia va mostrar una eficàcia d'extracció superior, aconseguint recuperar fins al 81 % del fòsfor p / Acevedo Juárez, B. (2016). Estudio y modelación matemática del cambio metabólico de las bacterias responsables de la eliminación biológica de fósforo en el tratamiento de aguas residuales [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/62585 / TESIS