Made available in DSpace on 2014-12-17T15:01:56Z (GMT). No. of bitstreams: 1 SyllosSS_TESE.pdf: 2557262 bytes, checksum: 77d0a0faa8e481b116f80dda9a4c8e96 (MD5) Previous issue date: 2013-07-01 / During production of oil and gas, there is also the production of an aqueous effluent called produced water. This byproduct has in its composition salts, organic compounds, gases and heavy metals. This research aimed to evaluate the integration of processes Induced Air Flotation (IAF) and photo-Fenton for reducing the Total Oils and Greases (TOG) present in produced water. Experiments were performed with synthetic wastewater prepared from the dispersion of crude oil in saline solution. The system was stirred for 25 min at 33,000 rpm and then allowed to stand for 50 min to allow free oil separation. The initial oil concentration in synthetic wastewater was 300 ppm and 35 ppm for the flotation and the photo-Fenton steps, respectively. These values of initial oil concentration were established based on average values of primary processing units in Potiguar Basin. The processes were studied individually and then the integration was performed considering the best experimental conditions found in each individual step. The separation by flotation showed high removal rate of oil with first-order kinetic behavior. The flotation kinetics was dependent on both the concentration and the hydrophilic-lipophilic balance (HLB) of the surfactant. The best result was obtained for the concentration of 4.06.10-3 mM (k = 0.7719 min-1) of surfactant EO 2, which represents 86% of reduction in TOG after 4 min. For series of surfactants evaluated, the separation efficiency was found to be improved by the use of surfactants with low HLB. Regarding the TOG reduction step by photo-Fenton, the largest oil removal reached was 84% after 45 min of reaction, using 0.44 mM and 10 mM of ferrous ions and hydrogen peroxide, respectively. The best experimental conditions encountered in the integrated process was 10 min of flotation followed by 45 min of photo-Fenton with overall TOG reduction of 99%, which represents 5 ppm of TOG in the treated effluent. The integration of processes flotation and photo-Fenton proved to be highly effective in reducing TOG of produced water in oilfields / Durante a produ??o de ?leo e g?s, ocorre tamb?m ? produ??o de uma corrente aquosa denominada ?gua de produ??o de petr?leo. Este subproduto apresenta em sua composi??o sais, compostos org?nicos, gases e metais pesados. Esta pesquisa buscou avaliar a integra??o dos processos de Flota??o por Ar Induzido (FAI) e foto-Fenton para a redu??o do Teor de ?leos e Graxas (TOG) presente em ?guas produzidas, visando recuperar ?leo presente na fase aquosa e mineralizar a carga org?nica remanescente. Os experimentos foram realizados com efluente sint?tico preparado a partir da dispers?o de petr?leo bruto em solu??o salina. O sistema foi agitado por 25 min a 33.000 rpm e depois deixado em repouso por 50 min para permitir a separa??o do ?leo livre. A concentra??o inicial de ?leo (TOG) no efluente sint?tico foi de 300 ppm e 35 ppm para as etapas de flota??o e de foto-Fenton, respectivamente. Estes valores iniciais de concentra??o de ?leo foram estabelecidos tomando com base a TOG m?dio do efluente nas unidades de processamento prim?rio da bacia Potiguar. Os processos foram estudados individualmente e, em seguida, realizada a integra??o considerando as melhores condi??es experimentais encontrada em cada etapa individualmente. A separa??o por flota??o apresentou elevada taxa de remo??o de ?leo com comportamento cin?tico de primeira ordem. A cin?tica de flota??o foi dependente tanto da concentra??o quanto do Balan?o Hidrof?lico-Lipof?lico (BHL) do tensoativo. O melhor resultado foi obtido para a concentra??o de 4,06.10-3 mM (k = 0,7719 min-1) do tensoativo EO 2, o que representa 86 % de redu??o do TOG ap?s 4 min de flota??o. Para a s?rie de tensoativos estudada, a efici?ncia de separa??o mostrou-se melhorada com o uso de tensoativo com menores BHL. Com respeito ? etapa de redu??o do TOG por foto-Fenton, a maior remo??o de ?leo alcan?ada foi de 84% ap?s 45 min de rea??o, utilizando 0,44 mM e 10 mM de ?ons ferrosos e per?xido de hidrog?nio, respectivamente. As melhores condi??es experimentais encontradas para os processos integrados foram 10 min de flota??o seguida de 45 min de foto-Fenton, com redu??o global de TOG de 99%, o que representa 5 ppm de TOG no efluente tratado. A integra??o dos processos flota??o e foto-Fenton mostrou ser altamente eficiente na redu??o de TOG em ?guas produzidas em campos de petr?leo

Made available in DSpace on 2016-12-23T14:41:52Z (GMT). No. of bitstreams: 1 Dissertacao de Luciana Brunhara Biazati.pdf: 848805 bytes, checksum: 4ed964a7ad50c362409f5ddb61fac503 (MD5) Previous issue date: 2009-03-06 / Os hidrocarbonetos policíclicos aromáticos (HPAs), derivados de petróleo, são substâncias cada vez mais preocupantes aos órgãos ambientais devido ao seu caráter tóxico, carcinogênico e mutagênico. Com o aumento da utilização de petróleo e seus derivados como fonte de energia, a contaminação do efluente líquido se expandiu, prejudicando a biota, incluindo seres humanos que de alguma forma fazem uso dessa água. É necessário que sejam desenvolvidos procedimentos eficazes na eliminação parcial ou total destes compostos. Uma técnica muito estudada atualmente no tratamento de efluentes líquidos é o processo Fenton. Ele se baseia na geração do radical hidroxila a partir da reação de íons Fe2+ e peróxido de hidrogênio. Devido ao seu elevado poder oxidante, o radical hidroxila degrada totalmente os compostos orgânicos, formando CO2, H2O e íons inorgânicos provenientes de heteroátomos. O presente trabalho estudou o processo Fenton na decomposição de HPAs (acenafteno, fluoreno, fluoranteno, benzo(a)pireno) em meio aquoso com a utilização de magnetitas puras ou dopadas com cobalto como fonte de íons Fe2+ e peróxido de hidrogênio. A análise da degradação e possível formação de intermediários foram acompanhadas por cromatografia gasosa/espectrometria de massa (CG/EM). Pôde-se observar que o percentual de degradação dos HPAs variou de 39 a 100%. O composto que mais degradou foi o acenafteno, com três anéis, enquanto que o benzo(a)pireno, com cinco anéis, teve a menor oxidação. Não foram encontrados intermediários acima do limite de detecção do equipamento. Além da CG/EM, foi utilizada a fluorescência como método de análise. O objetivo foi comparar a eficiência da magnetita pura e dopada com cobalto na degradação do fluoreno. Observou-se que o processo de degradação com a magnetita pura não foi significante. Já com a magnetita dopada com cobalto a degradação total ocorreu em cinco horas. Assim, o processo Fenton com utilização de magnetitas como fonte de ferro pode ser uma nova alternativa para o tratamento de HPAs em meio aquoso / The awareness regarding Polycyclics Aromatic Hydrocarbons (PAHs), petroleum derivatives, has been increasing over the years due to their toxic, carcinogenic and mutagenic characteristics. The increase on the use of petroleum and its derivatives as energy source has induced many accidents spilling liquid effluent in the environment, making harm to biota, including human beings. So that, developing efficient procedures is important on the partial or total elimination of these compounds. A common technique that has been used recently is the Fenton process. This is based on the generation of hydroxyl radical from the reaction of Fe2+ions and hydrogen peroxyde, forming CO2, H2O and inorganic ions from heteroatoms. This study evaluated PAHs (acenaphthene, fluorene, fluoranthene, benzo(a)pyrene) decomposition due to the fenton process in water by utilization of pure and doped magnetites (with Co as source of ions Fe2+) and hydrogen peroxyde. In order to compare the two kinds of magnetites, fluorene was degraded utilizing fluorescence to evaluate its concentration. We observed that reaction was not significant when pure magnetite was used, whereas doped one degraded fluorene completely after five hours. Because of this, only doped magnetite was used with the other compounds, but evaluating its efficience and intermadiaries formation by gas chromatography and mass spectrometry (GC/MS). The degradation of HPAs varied from 39 to 100%. Acenaphtene (with three rings) reacted more intensively whereas benzo(a)pyrene (with five) reacted less. No intermediate compounds were found above the detection limit. Beside GC-MS, fluorescence was utilized to analyse the compounds. Our goal was to compare the pure magnetite efficiency to that of doped one regarding fluorene degradation. We observed that the degradation using the former was not significant. Magnitite doped with cobalt degraded it within five hours. So, the method may be a new alternative of treating liquid efluents

Orientador: Wilson de Figueiredo Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-05T13:56:31Z (GMT). No. of bitstreams: 1 Arruda_TatianaLangbeckde_M.pdf: 1545576 bytes, checksum: 2e2b76b3f7f23e5e8b1087d0e9dc7912 (MD5) Previous issue date: 2005 / Mestrado / Quimica Analitica / Mestre em Química

O objetivo principal deste trabalho foi estudar a interferência de íons Cu2+ e Zn2+ na degradação do fenol pela reação de Fenton (Fe2+/Fe3+ + H2O2). Ambos os íons apresentaram efeito catalítico na reação de Fenton, porém atuam em etapas diferentes durante essa reação. Um dos primeiros intermediários da degradação, o catecol, é capaz de reduzir o Fe3+ a Fe2+, que, na presença de H2O2, cria um ciclo redox bastante eficiente. Portanto, este ciclo passa a ser o mecanismo principal da degradação térmica de fenol e seus produtos de oxidação nas etapas iniciais da reação. O íon Zn2+ interfere no tempo de persistência do catecol no meio reacional, provavelmente via estabilização do radical semiquinona correspondente. Um estudo da reação de cupro-Fenton (Cu2+ + H2O2) sugere dois possíveis papéis dos íons cobre: i) A reação de íons Cu1+ com H2O2 pode regenerar Cu2+ via uma reação análoga a de Fenton, formando radicais HO•. Na presença de um excesso de H2O2, o radical HO• pode ser consumido por outra molécula de H2O2 para produzir HOO•- e O2•-, (ii) Na etapa final da reação, quando o ferro(III) da solução é complexado na forma de ferrioxalato, os íons cobre assumem o papel de principal catalisador da degradação. Deste modo, a associação da reação de Fenton com a de cupro-Fenton resulta num aumento da eficiência global de mineralização do fenol / The principal objective of this work was a study of the interference of Cu2+ and Zn2+ ions on the degradation of phenol by the Fenton reaction (Fe2+/Fe3+ + H2O2). Both ions have a catalytic effect on the Fenton reaction, but act in different stages of the reaction. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+, which, in the presence of H2O2, forms an efficient catalytic redox cycle. Thus, this cycle becomes the principal route of thermal degradation of phenol and its oxidation products in the initial stages of the reaction. The Zn2+ interferes in the persistence time of catechol, probably via complexation with the corresponding semiquinone radical. A study of the cupro-Fenton reaction (Cu2+ + H2O2) suggests two principal modes of action of copper ions: (i) The reaction of Cu+ with H2O2 can regenerate Cu2+ via a reaction analogous to the Fenton reaction, forming the HO• radical. In the presence of excess H2O2, the HO• radical can react with another molecule of H2O2 to produce HOO•- and O2•-. (ii) In the final stages of the reaction, when the iron(III) in the solution is complexed in the form of ferrioxalate, the copper ions assume the role of the main catalyst of the degradation. As a result, the association of the Fenton reaction with the cupro-Fenton reaction leads to an overall improvement of the efficiency of the mineralization of phenol.

No caso de indústrias que utilizam processos de tingimento, a remoção da cor dos seus efluentes líquidos é uma grande preocupação. Os corantes azóicos representam 60% dos corantes utilizados na atualidade em todo o mundo; no entanto, são conhecidos pelo seu efeito carcinogênico e mutagênico, tornando-se urgente o seu tratamento. Assim sendo, tem surgido diversas alternativas aos processos convencionais de tratamento, relativamente aos processos de tratamento de efluentes convencionais, notadamente o processo Fenton, que se tem mostrado bastante promissor. Neste trabalho, investigou-se a otimização do processo Fenton, relativamente ao descoramento de dois corantes azóicos: a azorubina (C20H12N2Na2O7S2, C.I. 14720) e a tartrazina (C16H7N4Na3O9S2, C.I. 19140). Para tal, realizou-se um planejamento composto central, ajustou-se um modelo polinomial (empírico) aos dados experimentais obtidos e obtiveram-se as condições ótimas: razão [Fe2+]/[H2O2] = 0,64 e 0,32, pH = 1,5 e 2,8 e temperatura = 39°C. As variáveis-resposta foram: o grau de descoramento (medido pela área sob o espectro na região do visível) e as concentrações residuais de H2O2 (método do vanadato) e Fe (método da o-fenantrolina). Determinou-se o grau de mineralização por análises de carbono orgânico dissolvido e também a fitotoxicidade a sementes de alface (Lactuca sativa). Realizaram-se análises por CLAE-DAD de forma a se observar a geração dos produtos de oxidação. Obtiveram-se descoramentos de aproximadamente 100% para os corantes isoladamente e em mistura. As concentrações residuais de H2O2 e Fe foram desprezíveis. As mineralizações alcançadas foram da ordem de 50%. Observou-se um aumento de fitotoxicidade após o processo Fenton. Verificou-se, também, o desempenho do processo na presença de dois aditivos comumente usados na indústria têxtil, um igualizante e um anti-espumante. A presença dos aditivos reduziu significativamente os graus de descoramento (de 100% para 90%) e de mineralização (de 50% para 10%). Em relação à fitotoxicidade, verificou-se que os aditivos tornam as soluções muito tóxicas, não tendo sido observado um aumento estatisticamente significativo após o processo Fenton. As análises cromatográficas mostraram, inequivocamente, a presença de pelo menos um produto de oxidação nas amostras tratadas. Concluiu-se que o processo Fenton apresentou um ótimo desempenho para o descoramento dos corantes estudados. Entretanto, a presença dos aditivos tenderia a prejudicar o tratamento de efluentes que contivessem tais corantes. / In the case of industries that use dyeing processes, the removal of color from their wastewaters is a major concern. The azo dyes account for 60% of the dyes currently in use worldwide. However, they are known for their carcinogenic and mutagenic effects, making their treatment an urgent matter. Therefore, several alternatives to the conventional treatment processes have been devised, particularly the Fenton process, which has been proved to be very promising. In this work, the Fenton process optimization regarding the bleaching of two azo dyes was investigated: azorubine (C20H12N2Na2O7S2, C.I. 14720) and tartrazine (C16H7N4Na3O9S2, C.I. 19140). For that purpose, a central composite design was used, a polynomial (empiric) model was fitted to the experimental data, and the optimum conditions were determined: rate [Fe2+]/[H2O2] = 0.64 and 0.32, pH = 1.5 and 2.8, and temperature = 39°C. The response variables were: color removal (measured by the area under the spectrum obtained in the visible region) and the residual concentrations of H2O2 (vanadate method) and Fe (o-fenantroline method). It was determined the mineralization degree by dissolved organic carbon analyses and also the phytotoxicity to lettuce seeds (Lactuca sativa). HPLC-DAD analyses were performed in order to observe the generation of oxidation products. Color removals of approximately 100% were achieved for the each dyes and for a mixture of them. The residual concentrations of H2O2 and Fe were close to zero. Mineralizations around 50% were obtained and a phytotoxicity enhancement after Fenton\'s process. It has also been observed that the performance of that process in the presence of two textile auxiliary products (TAPs) commonly used, a leveling agent and an anti-foaming one. The auxiliaries reduced significantly color removal (from 100% to 90%) and the degree of mineralization (from 50% to 10%). Regarding the phytotoxicity, it was observed that the TAPs used rendered the solutions quite toxic, with no further statistically significant enhancement after the Fenton\'s process. The chromatographic analyses showed, undoubtedly, the presence of at least one oxidation product in the treated samples. It was concluded that the Fenton\'s process presented an excellent performance for removing the color of the studied dyes. However, the presence of the auxiliaries would tend to impair the treatment of wastewaters containing those dyes.

Orientador: Wilson de Figueiredo Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T12:42:03Z (GMT). No. of bitstreams: 1 Marques_EmanuelJoseNascimento_M.pdf: 2293976 bytes, checksum: 7be303ab6d3a366873fc9c1c636abfbf (MD5) Previous issue date: 2012 / Resumo: Neste trabalho foi avaliado um processo de lavagem de solo utilizando solução oxidante, visando a remediação de áreas contaminadas com hidrocarbonetos provenientes combustíveis. O processo foi denominado de lavagem oxidativa e consistiu na mistura de H2O2 com um catalisador de Fenton modificado, chamado Fentox®. A lavagem oxidativa foi aplicada em solo contaminado artificialmente com óleo diesel em laboratório, a fim de avaliar as mudanças ocorridas no perfil de distribuição dos hidrocarbonetos remanescentes no solo tratado e verificar as condições experimentais que resultassem em máxima remoção destes contaminantes. Foi possível obter remoção de 90% para alcanos totais, 69% para hidrocarbonetos policíclicos aromáticos (HPA) totais, e 86% para hidrocarbonetos totais de petróleo (HTP). O aumento na proporção entre fase líquida e fase sólida resultou em maior eficiência na remoção dos contaminantes. A lavagem do solo utilizando o agente tensoativo dodecil benzeno sulfonato de sódio (DBSS) foi outro aspecto investigado em laboratório. Verificou-se que em solo com baixa concentração inicial de HPA o uso do tensoativo não favoreceu a solubilização dos contaminantes. Além disso, a adição de tensoativo durante a lavagem oxidativa do solo não contribuiu para melhorar o desempenho do processo de remediação. O processo de lavagem oxidativa juntamente com solução de tensoativo foi aplicado em solo contaminado com óleos combustíveis em uma área localizada na cidade de São Paulo, a fim de remover os hidrocarbonetos presentes no local. Foi obtida redução de aproximadamente 87% do parâmetro HPA total, sendo que a extensão da remoção individual dos HPA apresentou variações, principalmente em função da hidrofobicidade característica de cada composto. A lavagem oxidativa mostrou-se uma alternativa viável sob o ponto de vista técnico, considerando que os resultados obtidos em campo foram comparáveis àqueles obtidos em laboratório / Abstract: In this work a soil washing process using oxidizing solution was evaluated, aiming the remediation of contaminated areas with hydrocarbons derived from fuels. The selected process was called oxidative soil washing and consists in the use of H2O2 with a modified Fenton¿s catalyst, called Fentox®. The oxidative washing was applied first in a laboratory diesel oil contaminated soil in order to evaluate changes in the distribution profile of hydrocarbons remaining in the treated soil and to set the experimental conditions that resulted in maximum removal of these contaminants. It was possible to obtain removals of 90% for total alkanes, 69% for polycyclic aromatic hydrocarbons (PAH), and 86% for total petroleum hydrocarbons (TPH). The increase in the liquid-solid ratio resulted in increase of the contaminant removal. The oxidative soil washing using the surfactant sodium dodecyl benzene sulphonate (SDBS) was another aspect investigated in the laboratory. It was found that in soil having low initial PAH concentration, the use of surfactant did not increase the contaminants solubilization. Furthermore, the surfactant addition during the soil oxidative washing did not improve the performance of the remediation process. The oxidative soil washing in the presence of the surfactant solution was applied in a fuel contaminated soil to remove hydrocarbons. Results indicated removal around 87 % for total PAH, with different rates according to the hydrophobicity of each compound. Oxidative soil washing proved to be a feasible alternative under the technical point of view, considering that results obtained on site were comparable to the ones obtained under laboratory conditions / Mestrado / Quimica Analitica / Mestre em Química

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The advanced oxidation protein products (AOPPs) are a new class of compounds identified as markers of oxidative damage to proteins. The physiology role of these products is not limited to assess the oxidative stress, and these products may actively participate in the inflammatory process, promoting different cell disorders, including induction of apoptosis and alterations in the processes of cell proliferation and differentiation. Myeloperoxidase (MPO)-derived hypochlorous acid (HOCl) produced by activated neutrophils contribute significantly to AOPP formation, and human serum albumin (HSA) is considered the main protein responsible for the generation of AOPPs However, the molecular composition of AOPPs is unclear. Additional pathways and protein targets for AOPP formation are largely unknown. The aim of this study was to induce the formation of AOPPs in vitro through Fenton reaction and to investigate whether this generation could be counteracted by N-acetylcysteine (NAC) and fructose-1,6-bisphosphate (FBP). In addition, this study aimed to examine whether AOPPs produced by Fenton reaction may induce the activation of the gene transcription of inflammatory molecules, including the nuclear factor-κB (NF-κB), cyclooxygenase-2 (COX-2) and interleukin-6 (IL-6) in human embryonic kidney cells (HEK 293). Additionally, it was investigated the collagen as a potential source of AOPPs via its exposure to HOCl. The HOCl-modified collagen stimulated the production of oxidants, such as HOCl and superoxide anion radical (O2 -), and pro-inflammatory agents, such as nitric oxide (NO) and AOPPs in human neutrophil. Furthermore, HOCl-modified collagen induced a decrease in cell viability and an increase of apoptosis in these cells. Finally, alpha-tocopherol inhibited the release of oxidants, decreased cell viability and apoptosis, suggesting a therapeutic potential means to prevent deleterious effects caused by AOPPs. Furthermore, these findings indicate that alternative pathways can form AOPPs, and these new products may contribute to the pathogenesis of several clinical conditions related to the accumulation of AOPPs. / Os produtos proteicos de oxidação avançada (AOPPs) são uma nova classe de compostos formados em consequência do estresse oxidativo e considerados biomarcadores úteis na detecção de dano oxidativo proteico. No entanto, o papel desses produtos não se limita apenas a refletir o grau oxidativo de proteínas, mas também podem participar de forma ativa no processo inflamatório, promovendo diferentes perturbações celulares, incluindo a indução de apoptose e alterações nos processos de proliferação e diferenciação celular. O principal mecanismo de formação dos AOPPs é através do ácido hipocloroso (HOCl) produzido pela enzima mieloperoxidase (MPO), sendo a albumina, a principal fonte proteica para a formação desses produtos. No entanto, a via MPO/HOCl parece não ser a única responsável pela formação de AOPPs, e uma série de estudos indicam que há vias alternativas que podem contribuir para formação de AOPPs. Outro fator importante, que também não está totalmente esclarecido, é se a albumina é a única proteína suscetível a formação dos AOPPs, uma vez que a composição molecular desses produtos ainda não está totalmente definida. Além dessas questões, é de interesse avaliar se os AOPPs formados por outra via mantém as características pró-infamatórias e pró-apoptóticas dos AOPPs originados pela via MPO/HOCl. Assim, o presente estudo teve como objetivo investigar se a reação de Fenton, importante geradora de radicais hidroxilas (OH ), é uma potencial via de formação de AOPPs, bem como se o colágeno, principal proteína da matriz extracelular, é uma proteína suscetível a formação desses produtos. Em um primeiro momento, foi demonstrado que a reação de Fenton induziu a formação de AOPPs e esse processo foi inibido por agentes antioxidantes, como N-acetilcisteína (NAC) e frutose-1,6-bisfosfato (FBP). Além disso, os AOPPs gerados através da reação de Fenton induziram um aumento da transcrição gênica de agentes envolvidos no processo inflamatório, incluindo o fator de transcrição κB (NF-κB), a cicloxigenase-2 (COX-2) e a interleucina-6 (IL-6), em células renais embrionárias (HEK 293) através de ensaio de transfecção celular e atividade da Luciferase. Outro importante achado deste estudo foi demonstrar que o colágeno exposto ao HOCl também é uma fonte proteica para a formação de AOPPs. Os AOPPs formados a partir do colágeno estimularam a produção de oxidantes, como o HOCl e radical ânion superóxido (O2 -), e de agentes inflamatórios, como óxido nítrico (NO) e AOPPs, em neutrófilos humanos isolados. Além disso, os AOPPs derivados do colágeno induziram uma diminuição da viabilidade celular e um aumento do processo apoptótico nessas células. Por fim, o alfa-tocoferol inibiu a liberação de oxidantes, preveniu a diminuição da viabilidade celular e o aumento do processo apoptótico, sugerindo que esse composto pode ser uma potencial ferramenta terapêutica para prevenir os efeitos deletérios promovidos pelos AOPPs. Do mesmo modo, esses achados indicam que os AOPPs podem ser formados por vias alternativas, e esses novos produtos podem contribuir na fisiopatogênese de diversas condições clínicas relacionadas com o acúmulo de AOPPs.

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.

La pollution des ressources en eau est un des défis importants auquel les Hommes doivent faire face. En particulier, de nouvelles solutions doivent émerger, puisque les techniques conventionnelles de traitement utilisées actuellement ne permettent pas une élimination efficace des divers polluants. Parmi les polluants émergents, les composés pharmaceutiques ont récemment été détectés dans différentes sources d'eau à travers le monde. Leurs effets indésirables sur l'environnement naturel et sur l'Homme ont déjà été reconnus mais doivent encore être éclaircis. De nombreux nouveaux procédés de traitement de l'eau apparaissent. En particulier, le procédé électro-Fenton a démontré sa capacité à éliminer les pharmaceutiques et autres contaminants persistants. Ce procédé est basé sur la génération in-situ d'une espèce oxydante très puissante, les radicaux hydroxyles (OH), qui permettent la dégradation non-sélective des polluants. Cependant, cela nécessite l'utilisation d'une quantité d'énergie importante, relativement coûteuse. Une solution viable est de coupler le procédé électro-Fenton avec un procédé biologique. En effet, l'utilisation de ce dernier est beaucoup plus économique, mais il possède une efficacité limitée envers les polluants persistants tels que les pharmaceutiques. Ainsi, le procédé hybride bio-électro-Fenton apparaît comme un bon compromis entre le coût et l'efficacité. Le but de cette thèse de doctorat a donc été d'optimiser le procédé électro-Fenton dans l'optique de le coupler avec un procédé biologique, afin d'éliminer les pharmaceutiques. Les principaux objectifs de cette étude reposent sur l'étude de l'influence des paramètres opératoires utilisés au cours du procédé électro-Fenton sur (a) la dégradation des pharmaceutiques ; (b) la minéralisation de la matière organique ; (c) l'évolution de la biodégradabilité; (d) la consommation énergétique. Cette thèse est composée de trois parties, au cours desquelles la complexité des solutions traitées a progressivement augmentée. Premièrement, une étude a été menée sur des solutions de produits pharmaceutiques seuls afin de mieux comprendre les mécanismes impliqués au cours de leur dégradation. La seconde partie porte sur l'étude expérimentale d'une solution synthétique composée d'un mélange de 13 pharmaceutiques. La dernière étape a consisté à mettre en place un procédé bio-électro-Fenton pour le traitement d'un effluent pharmaceutique réel. Cette démarche progressive a permis de mieux comprendre l'influence des paramètres opératoires utilisés au cours du procédé électro-Fenton. Les principaux résultats obtenus sont notamment l'optimisation de deux paramètres opératoires important : la concentration du catalyseur (Fe2+) et l'intensité du courant. L'influence de ces paramètres s'est révélée similaires au cours du traitement de tous les types de solution testée. Il a donc été possible de conclure que les valeurs optimales sont une concentration en Fe2+ de 0,2 mM et une intensité entre 100 et 500 mA. L'efficacité d'élimination des pharmaceutiques a été plus importante en utilisant des intensités plus faibles (100-300 mA). Cependant, la biodégradabilité de l'effluent, un paramètre important dans l'optique du post-traitement biologique, a été d'avantage augmentée en utilisant des intensités élevées (500-1000 mA). Par ailleurs, l'utilisation d'intensités élevées a aussi mené à augmenter la consommation énergétique, en particulier dans le cas de temps de traitement longs. Il apparaît donc évident qu'un compromis entre efficacité et consommation énergétique doit être trouvé pour chaque cas particulier et effluent à traiter. Pour conclure, les avancées de cette recherche sont principalement attribuées à la nouveauté de la combinaison bio-électro-Fenton. L'étude de l'influence des paramètres opératoires du procédé électro-Fenton a aussi permis d'améliorer la compréhension de cette nouvelle technique et contribue à son développement vers une application industrielle / Water pollution is one of the biggest challenges that humanity faces and combating it requires the development of treatment processes, as conventional methods used nowadays are no longer effective for the removal of various complex pollutants. Recently pharmaceuticals have been recognized to be contaminants of emerging environmental concern as their traces were detected in a spectrum of water bodies around the globe. The long term effects of their presence in a natural environment are not yet fully studied, but the potential outcomes can be detrimental to a sustainable future. Among the variety of currently rising treatment technologies, the electro-Fenton method, an electrochemical advanced oxidation process, has demonstrated an ability to eliminate pharmaceuticals as well as other types of persistent contaminants. This electrocatalytical process generates in situ strong oxidants species - hydroxyl radical (OH) - which non-selectively degrade organic pollutants. Due to the extensive cost in the application of electrical energy, its operation might be cost-prohibitive. A solution would be to combine it with biological processes which are more economically viable, but also less effective in the removal of pharmaceuticals. The combined process is expected to have a synergetic effect between cost and effectiveness. The goal of this PhD thesis is to optimize operating conditions of the electro-Fenton process for a feasible combination with a biological process as a means of treating pharmaceutical pollution. The main objectives addressed by this work are related to the influence of operating parameters of the electro-Fenton process on (a) removal of pharmaceuticals; (b) mineralization of organic matter; (c) enhancement of biodegradability; (d) energy consumption. The thesis has three distinct parts related to the type of treated aqueous solution. First, a mechanistic study was conducted on aqueous solutions of individual pharmaceuticals in order to understand general trends of their removal. Next, a series of experiments was carried out on a synthetic mixture of thirteen pharmaceuticals from different therapeutic classes. Lastly, laboratory bench-scale reactors of a combined bio-electro-Fenton process were operated for the treatment of real wastewater. The advance in the complexity of the treated solution allowed a comprehensive comparison and analysis of the influence of the operating parameters. The main results include the optimal values of two operating parameters: the catalyst (Fe2+) concentration and the applied current intensity for a given electro-Fenton setup. The effects of the operating parameters on the removal of pharmaceuticals and other organic matter were similar regardless of the treated solution. The optimal value for the Fe2+ concentration was concluded to be around 0.2 mM. The optimal current intensity was in the range 100-500 mA. The efficiency of the current in terms of the pharmaceuticals' removal was the highest with the lowest intensity (100-300 mA). At the same time the biodegradability, which was an important factor in the biological post-treatment process, improved with higher intensities of electric current (500-1000 mA). However, high current intensities resulted in an elevated energy consumption, particularly with a prolonged treatment time. A tradeoff would have to be consequently made between energy saving and the removal rates that should be found in any single case. The novelty of the research presented in this PhD thesis is firstly attributed to the novelty of the combination of electro-Fenton to a biological process. A detailed study of the influence of operating parameters of the electro-Fenton process on removal rates and biodegradability enhancement contributed not only to the general knowledge on the electro-Fenton process, but also to the advancement towards its upscaling and then further towards the industrial application of this technique

<p>Predmet&nbsp; izučavanja&nbsp; ove&nbsp; disertacije&nbsp; bio&nbsp; je&nbsp; ispitivanje&nbsp; mogućnosti&nbsp; kori&scaron;ćenja&nbsp; piritne&nbsp;izgoretine&nbsp; u&nbsp; tretmanu&nbsp; otpadnih&nbsp; voda&nbsp; tekstilne&nbsp; industrije&nbsp; kao&nbsp; i&nbsp; dalji&nbsp; tretman&nbsp; mulja&nbsp; nastalog&nbsp;nakon ovog procesa. Naime, nakon iskori&scaron;ćenja ovog otpada &nbsp;u Fenton procesima, iskori&scaron;ćena&nbsp;piritna izgoretina u najvećem procentu čini mulj koji zaostaje nakon tretmana. Kako se piritna&nbsp;ruda jo&scaron; u procesu proizvodnje sumporne kiseline&nbsp; koristi nepreči&scaron;ćena, zaostali&nbsp; mulj koji je&nbsp;potencijalno&nbsp; toksičan&nbsp; i&nbsp; ne&nbsp; može&nbsp; se&nbsp; direktno&nbsp; odlagati&nbsp; bez&nbsp; prethodnog&nbsp; tretmana.&nbsp; Stoga,&nbsp;primenjena&nbsp; je&nbsp; tehnika&nbsp; stabilizacija&nbsp; i&nbsp; solidifikacija&nbsp; (S/S)&nbsp; uz&nbsp; kori&scaron;ćenje&nbsp; portland&nbsp; cementa,&nbsp;kalcijum-oksida, prirodnog zeolita, letećeg pepela, kaolinita,&nbsp; bentonita i&nbsp; autohtone&nbsp; gline &nbsp;za&nbsp;imobilizaciju metala. Istraživanja u ovoj disertaciji vr&scaron;ena su u dve faze. Prva faza imala je za&nbsp;cilj&nbsp; optimizaciju&nbsp; operativnih&nbsp; uslova&nbsp; Fenton&nbsp; tretmana&nbsp; pri&nbsp; kojima&nbsp; se&nbsp; postiže&nbsp; najvi&scaron;i&nbsp; stepen&nbsp;obezbojavanja&nbsp; i&nbsp; mineralizacije&nbsp; ispitivanih&nbsp; efluenata.&nbsp; Takođe&nbsp; ispitivanje&nbsp; je&nbsp; uključilo&nbsp; i&nbsp;karakterizaciju nastalih efluenata kako bi se procenila efikasnost primenjenog, i mogućnost&nbsp;daljeg&nbsp; tretmana.&nbsp; Druga&nbsp; faza&nbsp; uključivala&nbsp; je&nbsp; karakterizaciju&nbsp; nastalog&nbsp; mulja&nbsp; nakon&nbsp; tretmana&nbsp;obojenih&nbsp; efluenata&nbsp; i&nbsp; njegov&nbsp; tretman&nbsp; solidifikacijom&nbsp; i&nbsp; stabilizacijom.&nbsp; Vr&scaron;eno&nbsp; je&nbsp; određivanje&nbsp;efikasnosti&nbsp; primenjenih&nbsp; imobilizacionih&nbsp; agenasa&nbsp; u&nbsp; S/S tretmanu&nbsp; i&nbsp; dominantnog&nbsp; mehanizma&nbsp;<br />izluživanja&nbsp; metala&nbsp; koji&nbsp; opisuju&nbsp; njihov&nbsp; transport&nbsp; iz&nbsp; dobijenih&nbsp; solidifikata.&nbsp; Primenjeni&nbsp; su&nbsp; i&nbsp;modifikovani&nbsp; testovi&nbsp; izluživanja&nbsp; sa&nbsp; ciljem&nbsp; &scaron;to&nbsp; bolje&nbsp; simulacije&nbsp; realnih&nbsp; uslova.&nbsp; Rezultati&nbsp;dobijeni&nbsp; simulacijom&nbsp; uslova&nbsp; će&nbsp; dalje&nbsp; omogućiti&nbsp; modelovanje&nbsp; pona&scaron;anja&nbsp; metala&nbsp; u&nbsp; smislu&nbsp;dugoročnog&nbsp; &quot;izluživanja&quot;&nbsp; iz&nbsp; tretiranog&nbsp; otpada&nbsp; kao&nbsp; i&nbsp; procenu&nbsp; najefikasnijih&nbsp; agenasa&nbsp; za&nbsp;imobilizaciju različitih metala u ovom tipu otpada. TakoĎe primenjeni su testovi izluživanja&nbsp;sa jednom ekstrakcijom kako bi se osiguralo&nbsp; slaganje rezultata sa maksimalno dozvoljenim&nbsp;koncentracijama&nbsp; aktuelnih&nbsp; pravilnika.&nbsp; Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata&nbsp; zaključeno&nbsp; je&nbsp; da&nbsp; se&nbsp;piritna izgoretina može uspe&scaron;no koristiti kao izvor katalitičkog gvožđa u Fenton tretmanima&nbsp;obojenih&nbsp; efluenata&nbsp; i&nbsp; može&nbsp; se&nbsp; smatrati&nbsp; efektivnom&nbsp; metodom &nbsp; predtretmana&nbsp; za&nbsp;nebiodegradabilne&nbsp; otpadne&nbsp; vode,&nbsp; čineći&nbsp; ih&nbsp; pogodnijim&nbsp; za&nbsp; konvencionalni&nbsp; biolo&scaron;ki&nbsp; tretman.&nbsp;Takođe&nbsp; u&nbsp; drugoj&nbsp; fazi&nbsp; istraživanja,&nbsp; na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata,&nbsp; zaključeno&nbsp; je&nbsp; da&nbsp; je&nbsp; mulj&nbsp;tertian&nbsp; sa&nbsp; navedenim&nbsp; imobilizacionim&nbsp; agensima&nbsp; uspe&scaron;no&nbsp; solidifikovan&nbsp; i&nbsp; stabilizovan&nbsp;materijal.&nbsp; Optimalane&nbsp; su&nbsp; sme&scaron;e&nbsp; koje&nbsp; kao&nbsp; jedan&nbsp; od&nbsp; imobilizacionih&nbsp; agenasa&nbsp; sadrže&nbsp; leteći&nbsp;<br />pepeo, prevashodno u kombinaciji sa cementom i krečom. Dobijeni podaci su &nbsp;neprocenjivi sa&nbsp;aspekta ekonomski i ekolo&scaron;ki prihvatljivog upravljanja opasnim industrijskim otpadom.&nbsp;</p> / <p>This work is concerned with exploring the possibility of using pyrite cinders in the treatment&nbsp;of&nbsp; textile&nbsp; industry&nbsp; effluents&nbsp; and&nbsp; further&nbsp; treatment&nbsp; of&nbsp; sludge&nbsp; generated&nbsp; after&nbsp; this&nbsp; process.&nbsp;Namely,&nbsp; after&nbsp; the&nbsp; utilization&nbsp; of&nbsp; this&nbsp; waste&nbsp; in&nbsp; Fenton&nbsp; processes&nbsp; slag&nbsp; that&nbsp; remains&nbsp; after&nbsp;treatment is mostly composed of used pyrite cinder. As the pyrite ore, in the production of&nbsp;sulfuric&nbsp; acid,&nbsp; is&nbsp; used&nbsp; untreated,&nbsp; sludge&nbsp; that&nbsp; remains&nbsp; is&nbsp; potentially&nbsp; toxic&nbsp; and&nbsp; cannot&nbsp; be&nbsp;disposed&nbsp; directly&nbsp; without&nbsp; treatment.&nbsp; Therefore,&nbsp; the&nbsp; stabilization&nbsp; and&nbsp; solidification&nbsp; (S/S)&nbsp;technique&nbsp; with&nbsp; the&nbsp; usage&nbsp; of&nbsp; portland&nbsp; cement,&nbsp; calcium&nbsp; oxide,&nbsp; zeolite,&nbsp; fly&nbsp; ash,&nbsp; kaolinite,&nbsp;bentonite and native clay was used for metal immobilization. The research in this dissertation&nbsp;was carried out in two phases. The first phase aimed to optimize the operational conditions of&nbsp;Fenton&nbsp; treatment&nbsp; in&nbsp; which&nbsp; the&nbsp; highest&nbsp; degree&nbsp; of&nbsp; decolourization&nbsp; and&nbsp; mineralization&nbsp; was&nbsp;achieved in tested effluents. Also the research has included the characterization of generated&nbsp;effluents in order to evaluate the effectiveness of the treatment applied, and the possibility of&nbsp;further&nbsp; treatment.&nbsp; The&nbsp; second&nbsp; phase&nbsp; involved&nbsp; the&nbsp; characterization&nbsp; of&nbsp; the&nbsp; generated&nbsp; sludge&nbsp;after the treatment of effluents that contained dyes and its treatment with solidification and&nbsp;stabilization technique.&nbsp; The determination of used immobilization agents effectiveness was&nbsp;Conducted&nbsp; to&nbsp; determine&nbsp; the&nbsp; efficacy&nbsp; of&nbsp; immobilization&nbsp; agents&nbsp; in&nbsp; S&nbsp; /&nbsp; S&nbsp; treatment&nbsp; and&nbsp; the&nbsp;dominant&nbsp; mechanism&nbsp; of&nbsp; leaching&nbsp; of&nbsp; metals&nbsp; that&nbsp; describe&nbsp; their&nbsp; transport&nbsp; from&nbsp; the&nbsp; received&nbsp;solidificate . Were applied and modified leaching tests with the aim of better simulation of&nbsp;real&nbsp; conditions.&nbsp; The&nbsp; results&nbsp; obtained&nbsp; by&nbsp; condition&nbsp; simulation&nbsp; will&nbsp; enable&nbsp; the&nbsp; modeling&nbsp; of&nbsp;behavior of metals in terms of long-term leaching period from the treated sludge and assess&nbsp;the most effective agents for the immobilization of various metals in this type of waste. Also,&nbsp;single-extraction leaching tests were applied to ensure the accordance of obtained results &nbsp;with&nbsp;the maximum permissible concentrations of current regulations. Based on these results, it was&nbsp;concluded&nbsp; that&nbsp; the&nbsp; pyrite&nbsp; cinders&nbsp; can&nbsp; be&nbsp; successfully&nbsp; used&nbsp; as&nbsp; a&nbsp; source&nbsp; of&nbsp; catalytic&nbsp; iron&nbsp; in&nbsp;Fenton&nbsp; treatment&nbsp; of&nbsp; effluents&nbsp; containing&nbsp; dyes,&nbsp; and&nbsp; can&nbsp; be&nbsp; considered&nbsp; an&nbsp; effective&nbsp;pretreatment&nbsp; method&nbsp; for&nbsp; non-biodegradable&nbsp; waste&nbsp; waters,&nbsp; making&nbsp; them&nbsp; amenable&nbsp; to&nbsp;conventional biological treatment. Also in the second phase, based on the results obtained, it&nbsp;was concluded that the sludge treated with&nbsp; aforementioned&nbsp; immobilization agents represents&nbsp;a successfully solidified and stabilized material. The optimal mixtures are those that contain&nbsp;fly ash as one of the used immobilization agents, primarily in combination with cement and&nbsp;lime.&nbsp; The&nbsp; obtained&nbsp; data&nbsp; are&nbsp; invaluable&nbsp; in&nbsp; terms&nbsp; of&nbsp; economic&nbsp; and&nbsp; environmentally&nbsp; sound&nbsp;management of hazardous industrial waste.</p>