Orientador: Nelson Eduardo Duran Caballero / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-05T10:31:57Z (GMT). No. of bitstreams: 1 Assalin_MarciaRegina_D.pdf: 6063801 bytes, checksum: 275c581d4250a4932181e1314febc995 (MD5) Previous issue date: 2005 / Resumo: Neste trabalho foram estudados diversos aspectos de aplicação dos processos químicos (ozônio) e biológico (lodo ativado), aplicados de maneira isolada e combinada no tratamento do efluente papeleiro Kraft E1. A caracterização do efluente Kraft E1 foi realizada frente a vários parâmetros físico-químicos: fenóis totais, cor, carbono orgânico total (COT), demanda química de oxigênio (DQO), além da toxicidade frente a alga Selenastrum capricornutum. A eficiência dos processos estudados foi avaliada frente a redução de valores dos parâmetros de caracterização. As melhores condições de ozonização para o tratamento do efluente Kraft E1 foram pH 10 e 14 mg L de O3, por até 60 minutos de tratamento. Observou-se que a ozonização aplicada em meio fortemente alcalino (pH > 10) resulta num menor consumo de ozônio, o que pode ser relacionado com uma cinética de degradação mais lenta. O tratamento com ozônio mostrou maior eficiência para a remoção de cor, fenóis totais e toxicidade do efluente papeleiro. O processo biológico realizado num tempo de retenção hidraúlica (TRH) igual a 12 h, foi bastante eficiente na degradação da matéria orgânica do efluente. A remoção da cor e fenóis totais por este processo foi bastante afetada pelo TRH aplicado, o que não ocorreu com a remoção de carga orgânica. O processo combinado Iodo ativado (12 h) - ozônio (30 minutos) foi o que apresentou os melhores resultados para o tratamento do efluente papeleiro (DQO 75 %; COT 73 %, COR 80,7 % e fenóis totais 66,9 %). / Abstract: The efficiency of combined chemical (ozone) and biological (activated sludge) process in the treatment of Kraft E1 mill effluent was studied. The reduction of total phenols, color, total organic carbon (TOC), chemical oxygen demand (COD) and the toxicity (Selenastrum capricornutum) was evaluated. Different doses of ozone and pH of the effluent were studied. Treatment using pH 10 and concentration of 14 mg L of O3 in 60 min were the most efficient in the total phenols and color removal, but the results indicated negligible TOC reduction by application of the ozonation processes. The increase of pH as the reduction of ozone concentration influenced the kinetics properties of the process. The activated sludge process, (hydraulic retention time -HRT 12 h) was the most efficient for the TOC removal. Degradation of total phenolic compounds and decoloration were seriously affected by HRT variation. The combined process activated sludge (12 h) - ozonation (30 minutes) showed good results for the treatment of the Kraft E1 effluent (COD 75 %; TOC 73 %, Decoloration 80,7 % and Total Phenols 66,9 %). / Doutorado / Físico-Química / Doutor em Ciências

La présence des antibiotiques à usage humain et vétérinaire dans l’écosystème aquatique, est devenue un problème écologique sérieux. En effet, ces substances résistent aux traitements des stations d’épuration, ce qui engendre leur introduction et accumulation dans l’environnement. Par conséquent, le développement de méthodes efficaces pour le traitement de ces polluants est nécessaire. La première partie de ce travail de thèse s’inscrit dans le cadre de la dégradation des antibiotiques par procédé électro-Fenton. Ce procédé consiste à produire in situ des espèces fortement oxydantes, les radicaux hydroxyle, permettant la dégradation totale des composés organiques persistants. La sulfaméthazine (SMT) et le triméthoprime (TMP) ont été choisis comme composés modèles, en raison de leur détection régulière dans les effluents des stations d’épuration, les eaux de surface et les eaux souterraines. Dans cette première partie, nous avons examiné l’influence de différents paramètres expérimentaux, sur l’efficacité du procédé électro-Fenton. Les conditions opératoires optimales nécessaires pour la dégradation totale des deux antibiotiques étudiés, ont été également déterminées. En outre, les produits intermédiaires aromatiques générés lors de la dégradation des deux antibiotiques, ont été identifiés. Leur évolution durant l’électrolyse a été également suivie. La deuxième partie est consacrée à l’étude de la minéralisation de la SMT et du TMP par procédé électro-Fenton. Les résultats obtenus indiquent que les taux de minéralisation de la SMT et du TMP sont respectivement de 91 et 85% après dix-huit heures de traitement. Les acides carboxyliques formés, ainsi que les ions inorganiques libérés ont été identifiés, leur évolution a été suivie au cours du traitement. De plus, en se basant sur les différents sous-produits générés, nous avons proposé des mécanismes réactionnels pour la minéralisation de la SMT et du TMP par procédé électro-Fenton. La troisième partie de ce travail porte sur l’étude de la minéralisation des deux antibiotiques considérés par couplage du procédé électro-Fenton et d’un traitement biologique. La SMT et le TMP, ont été prétraités par procédé électro-Fenton, ce qui a conduit à leur dégradation totale, avec des taux de minéralisation faibles. Par la suite, un traitement biologique a été effectué durant 20 jours, les taux globaux de minéralisation ont alors augmenté pour atteindre 81 et 68% pour respectivement la SMT et le TMP. Dans une dernière partie, nous avons procédé à la minéralisation de deux effluents industriels, contenant les antibiotiques étudiés, par couplage du procédé électro-Fenton et d’un traitement biologique. Les taux de minéralisation globaux obtenus sont de 81 et 89% pour respectivement l’effluent SMT et l’effluent TMP. Ce qui prouve la pertinence du procédé combiné, pour le traitement des effluents industriels. / The occurrence of human and veterinary antibiotics in the aquatic ecosystem becomes a serious environmental problem. These compounds cannot be treated by wastewater treatment plants, resulting in their entry and accumulation to measurable levels in the environment. Over the last decade, the conventional biological processes were used for wastewater treatment, but did not appear to be enough effective when dealing with wastes containing antibiotics, owing to the important recalcitrance of these compounds. Therefore, the development of efficient methods to treat antibiotics is needed. The first part of this thesis is focused on the degradation of antibiotics by electro-Fenton process. This process consists in producing in situ strongly oxidizing species, hydroxyl radicals, allowing the total degradation of persistent and toxic organic compounds. Sulfamethazine (SMT) and trimethoprim (TMP) were selected as model compounds, because of their regular detection in the effluents of sewage plants, surface water and groundwater. In this first part, we examined the influence of various operating parameters, on the efficiency of electro-Fenton process. The optimal operating conditions necessary for the removal of the studied antibiotics, were also determined. Moreover, the aromatic intermediate products, generated during antibiotics degradation, were identified. Their evolution during electrolysis was also followed. The second part is devoted to the study of mineralization, of SMT and TMP, by the electro-Fenton process. The obtained results indicate that the yields of SMT and TMP mineralization were 91 and 85%, respectively after eighteen hours of treatment. The identification and monitoring of short chain carboxylic acids and released inorganic ions during the treatment, were carried out. Furthermore, based on the identified by-products, we proposed a plausible mineralization reaction pathway for SMT and TMP. The third part of this work concerns the study of the mineralization of considered antibiotics by a combined process coupling an electro-Fenton pretreatment and a biological degradation. SMT and TMP were pretreated by the electro-Fenton process, which led to their total degradation, with low levels of mineralization, ensuring significant residual organic content for a subsequent biological treatment. Afterwards, biological treatment was performed during 20 days and showed that the level of overall mineralization increased to reach 81 and 68% for SMT and TMP, respectively. In a last part, we carried out the mineralization of two industrial effluents containing SMT and TMP, by combining electro-Fenton and activated sludge treatment. Overall mineralization yields of the combined process of 81 and 89% were obtained for SMT effluent and TMP effluent, respectively. This result confirms the relevance of combined process, even for the treatment of industrial effluents.

Made available in DSpace on 2017-07-10T19:25:20Z (GMT). No. of bitstreams: 1 Cristiane.pdf: 2244710 bytes, checksum: 7f1fb544f09e13f94b271e1202243132 (MD5) Previous issue date: 2012-02-13 / In this study, it was evaluated the operational conditions, the organic matter, nitrogen and phosphorus removal efficiency and the hydrodynamic behavior of a continuously up-flow combined anaerobic-aerobic fixed bed reactor (RAALF), operated in bench-scale, filled with expanded clay and polyurethane foam cubic arrays as means of biomass immobilization support, in the treatment of raw effluent from a cattle slaughterhouse. Three different operational conditions were tested: Step I, characterized by the operation of RAALF in anaerobic condition; Step II, in combined condition (anaerobic-aerobic), and Step III, in combined condition with recirculation. In each operational step three different hydraulic retention times (14, 11 and 8 h) were tested. The hydrodynamics assays were determined using stimulus-response type pulse, with Eosina Y as a tracer to obtain the curves of residence time distribution (RTD). The results from the RAALF in the Step I, under anaerobic condition, indicated that operational conditions ensured the process of anaerobic digestion, with keeping of the pH and the RAALF s buffering, promoting a biochemical balance between acidogenic/acetogenic and methanogenic archaea. In this operational step, the HRT of 11 h showed better result, with removal efficiency of raw COD, filtered COD, TS, TSS and N-amon of 59, 60, 56, 76 and 16%, respectively. In Step II, the HRT of 14 h showed better results in terms of organic matter and solids removal efficiency, with 58, 66, 66 and 84% for raw COD, filtered COD, TS and TSS, respectively. The overall efficiency of nitrogen removal achieved in this study was 0, 17 and 7% at Step I; 37, 22 and 22% in Step II for the HRT 14, 11 and 8 h, respectively, and 50 and 29% for the HDT of 11 and 8 h in Step III. Therefore, there was an evolution in the overall nitrogen removal efficiency in Steps II and III when compared to Step I, due to the partial nitrification and denitrification. Denitrification has been compromised by factors such as liquid temperature, pH, and DQO/N-NO3- ratio. The efficiency of phosphorus removal was 0, 0 and 15% in Step I and 46, 0 and 0% in Step II for HRT 14, 11 and 8 h, respectively, and 10 and 0 % removal HRT to 11 and 8 h, respectively, in Step III. The ANOVA and Tukey tests indicated that the operational stages I, II and III were statistically different for all physical-chemical parameters evaluated, except for phosphorus, for which it can be stated that the efficiency of organic matter and nitrogen removal was affected by the operating condition. The hydrodynamic study conducted at RAALF indicated behavior tending to a complete mixing and deviations from ideality were found, such as dead zones, recirculation and long tail effect. The dispersion degrees were probably influenced by insertion of the aerobic phase, which improved the liquid mixture inside the reactor. The RAALF presented similar kinetic behavior in the operational steps I, II and III, represented by the first order model, with increase of k and vr parameters along the height of the anaerobic phase and decrease of the kinetic constant and degradation rate in the aerobic phase / Neste trabalho foram avaliadas as condições operacionais, a eficiência de remoção de matéria orgânica, nitrogênio e fósforo e o comportamento hidrodinâmico de um reator anaeróbio aeróbio de leito fixo (RAALF) e fluxo ascendente, vertical, operado de modo contínuo, em escala de bancada, preenchido com argila expandida e matrizes cúbicas de espuma de poliuretano como meio suporte para imobilização da biomassa, no tratamento de efluente bruto proveniente de um matadouro bovino. Foram testadas três condições operacionais distintas, sendo a Etapa I caracterizada pela operação do RAALF em condição anaeróbia, a Etapa II em condição combinada (anaeróbia-aeróbia) e a Etapa III em condição combinada com recirculação. Em cada etapa operacional foram testados três tempos de detenção hidráulicos diferentes (14, 11 e 8 h). O comportamento hidrodinâmico foi avaliado utilizando ensaios de estímulo-resposta, tipo pulso, com o uso de Eosina Y como traçador para obtenção das curvas de distribuição do tempo de residência (DTR). Os resultados da avaliação do RAALF na Etapa I, sob condição anaeróbia, indicaram que as condições operacionais garantiram o processo de digestão anaeróbia, com a manutenção do pH e tamponamento do sistema, promovendo um equilíbrio bioquímico entre microrganismos acidogênicos/acetogênicos e arqueas metanogênicas. Nesta etapa operacional, o TDH de 11 h apresentou melhores rendimentos, com eficiência de remoção de DQO bruta, DQO filtrada, ST, SST e N-amon de 59, 60, 56, 76 e 16%, respectivamente. Na Etapa II, o TDH de 14 horas apresentou melhores resultados em termos de eficiência de remoção de matéria orgânica e sólidos, com valores de 58, 66, 66 e 84% para DQO bruta, DQO filtrada, ST e SST, respectivamente. A eficiência global de remoção de nitrogênio alcançada neste estudo foi de 0, 17 e 7% na Etapa I, 37, 22 e 22% na Etapa II, para o TDH de 14, 11 e 8 h, respectivamente, e de 50 e 29% para o TDH de 11 e 8 h na Etapa III; portanto, verifica-se evolução da eficiência global na remoção de nitrogênio das Etapas II e III se comparada à Etapa I, decorrente do processo de nitrificação e desnitrificação parcial. A desnitrificação foi comprometida por fatores como temperatura do líquido, pH e relação DQO/N-NO3-. As eficiências de remoção de fósforo total foram de 0, 0 e 15% na Etapa I e de 46, 0 e 0% na Etapa II para os TDHs de 14, 11 e 8 h, respectivamente, e de 10 e 0% de remoção para o THD de 11 e 8 h, respectivamente, na Etapa III. O teste ANOVA e o teste Tukey indicaram que as etapas operacionais I, II e III foram estatisticamente diferentes entre si, para todos os parâmetros físico-químicos avaliados, com exceção do fósforo, podendo-se afirmar que a eficiência de remoção de matéria orgânica e nitrogenada foi afetada pela condição operacional. O estudo hidrodinâmico realizado no RAALF indicou comportamento tendendo ao de mistura completa e foram constatados desvios de idealidade, como zonas mortas, recirculações e efeito de cauda longa. Os graus de dispersão foram possivelmente influenciados pela inserção da fase aeróbia, que promoveu uma melhor mistura do líquido no interior do reator. O RAALF apresentou comportamento cinético similar nas etapas operacionais I, II e III, representado pelo modelo de primeira ordem, com aumento dos parâmetros k e vr ao longo da altura da fase anaeróbia, e diminuição da constante cinética e da velocidade de degradação na fase aeróbia

Made available in DSpace on 2017-05-12T14:48:43Z (GMT). No. of bitstreams: 1 Cristiane.pdf: 2244710 bytes, checksum: 7f1fb544f09e13f94b271e1202243132 (MD5) Previous issue date: 2012-02-13 / In this study, it was evaluated the operational conditions, the organic matter, nitrogen and phosphorus removal efficiency and the hydrodynamic behavior of a continuously up-flow combined anaerobic-aerobic fixed bed reactor (RAALF), operated in bench-scale, filled with expanded clay and polyurethane foam cubic arrays as means of biomass immobilization support, in the treatment of raw effluent from a cattle slaughterhouse. Three different operational conditions were tested: Step I, characterized by the operation of RAALF in anaerobic condition; Step II, in combined condition (anaerobic-aerobic), and Step III, in combined condition with recirculation. In each operational step three different hydraulic retention times (14, 11 and 8 h) were tested. The hydrodynamics assays were determined using stimulus-response type pulse, with Eosina Y as a tracer to obtain the curves of residence time distribution (RTD). The results from the RAALF in the Step I, under anaerobic condition, indicated that operational conditions ensured the process of anaerobic digestion, with keeping of the pH and the RAALF s buffering, promoting a biochemical balance between acidogenic/acetogenic and methanogenic archaea. In this operational step, the HRT of 11 h showed better result, with removal efficiency of raw COD, filtered COD, TS, TSS and N-amon of 59, 60, 56, 76 and 16%, respectively. In Step II, the HRT of 14 h showed better results in terms of organic matter and solids removal efficiency, with 58, 66, 66 and 84% for raw COD, filtered COD, TS and TSS, respectively. The overall efficiency of nitrogen removal achieved in this study was 0, 17 and 7% at Step I; 37, 22 and 22% in Step II for the HRT 14, 11 and 8 h, respectively, and 50 and 29% for the HDT of 11 and 8 h in Step III. Therefore, there was an evolution in the overall nitrogen removal efficiency in Steps II and III when compared to Step I, due to the partial nitrification and denitrification. Denitrification has been compromised by factors such as liquid temperature, pH, and DQO/N-NO3- ratio. The efficiency of phosphorus removal was 0, 0 and 15% in Step I and 46, 0 and 0% in Step II for HRT 14, 11 and 8 h, respectively, and 10 and 0 % removal HRT to 11 and 8 h, respectively, in Step III. The ANOVA and Tukey tests indicated that the operational stages I, II and III were statistically different for all physical-chemical parameters evaluated, except for phosphorus, for which it can be stated that the efficiency of organic matter and nitrogen removal was affected by the operating condition. The hydrodynamic study conducted at RAALF indicated behavior tending to a complete mixing and deviations from ideality were found, such as dead zones, recirculation and long tail effect. The dispersion degrees were probably influenced by insertion of the aerobic phase, which improved the liquid mixture inside the reactor. The RAALF presented similar kinetic behavior in the operational steps I, II and III, represented by the first order model, with increase of k and vr parameters along the height of the anaerobic phase and decrease of the kinetic constant and degradation rate in the aerobic phase / Neste trabalho foram avaliadas as condições operacionais, a eficiência de remoção de matéria orgânica, nitrogênio e fósforo e o comportamento hidrodinâmico de um reator anaeróbio aeróbio de leito fixo (RAALF) e fluxo ascendente, vertical, operado de modo contínuo, em escala de bancada, preenchido com argila expandida e matrizes cúbicas de espuma de poliuretano como meio suporte para imobilização da biomassa, no tratamento de efluente bruto proveniente de um matadouro bovino. Foram testadas três condições operacionais distintas, sendo a Etapa I caracterizada pela operação do RAALF em condição anaeróbia, a Etapa II em condição combinada (anaeróbia-aeróbia) e a Etapa III em condição combinada com recirculação. Em cada etapa operacional foram testados três tempos de detenção hidráulicos diferentes (14, 11 e 8 h). O comportamento hidrodinâmico foi avaliado utilizando ensaios de estímulo-resposta, tipo pulso, com o uso de Eosina Y como traçador para obtenção das curvas de distribuição do tempo de residência (DTR). Os resultados da avaliação do RAALF na Etapa I, sob condição anaeróbia, indicaram que as condições operacionais garantiram o processo de digestão anaeróbia, com a manutenção do pH e tamponamento do sistema, promovendo um equilíbrio bioquímico entre microrganismos acidogênicos/acetogênicos e arqueas metanogênicas. Nesta etapa operacional, o TDH de 11 h apresentou melhores rendimentos, com eficiência de remoção de DQO bruta, DQO filtrada, ST, SST e N-amon de 59, 60, 56, 76 e 16%, respectivamente. Na Etapa II, o TDH de 14 horas apresentou melhores resultados em termos de eficiência de remoção de matéria orgânica e sólidos, com valores de 58, 66, 66 e 84% para DQO bruta, DQO filtrada, ST e SST, respectivamente. A eficiência global de remoção de nitrogênio alcançada neste estudo foi de 0, 17 e 7% na Etapa I, 37, 22 e 22% na Etapa II, para o TDH de 14, 11 e 8 h, respectivamente, e de 50 e 29% para o TDH de 11 e 8 h na Etapa III; portanto, verifica-se evolução da eficiência global na remoção de nitrogênio das Etapas II e III se comparada à Etapa I, decorrente do processo de nitrificação e desnitrificação parcial. A desnitrificação foi comprometida por fatores como temperatura do líquido, pH e relação DQO/N-NO3-. As eficiências de remoção de fósforo total foram de 0, 0 e 15% na Etapa I e de 46, 0 e 0% na Etapa II para os TDHs de 14, 11 e 8 h, respectivamente, e de 10 e 0% de remoção para o THD de 11 e 8 h, respectivamente, na Etapa III. O teste ANOVA e o teste Tukey indicaram que as etapas operacionais I, II e III foram estatisticamente diferentes entre si, para todos os parâmetros físico-químicos avaliados, com exceção do fósforo, podendo-se afirmar que a eficiência de remoção de matéria orgânica e nitrogenada foi afetada pela condição operacional. O estudo hidrodinâmico realizado no RAALF indicou comportamento tendendo ao de mistura completa e foram constatados desvios de idealidade, como zonas mortas, recirculações e efeito de cauda longa. Os graus de dispersão foram possivelmente influenciados pela inserção da fase aeróbia, que promoveu uma melhor mistura do líquido no interior do reator. O RAALF apresentou comportamento cinético similar nas etapas operacionais I, II e III, representado pelo modelo de primeira ordem, com aumento dos parâmetros k e vr ao longo da altura da fase anaeróbia, e diminuição da constante cinética e da velocidade de degradação na fase aeróbia