DMSO (dimethyl sulfoxide) is a liquid with a high boiling point (189 oC) that has been extensively utilized in various industries owing to its ability to dissolve various organic and inorganic compounds. DMSO is increasingly being adopted as a detergent or a photo-resistant stripping solvent in manufacturing semiconductors and liquid crystal displays (LCD). Therefore, DMSO is now a major component of wastewater. The biological treatment of DMSO-containing wastewater generates noxious DMS (dimethyl sulfide) and other compounds that may cause odor problems. Also having a high water solubility and a moderate boiling point (110 oC), tetrafluoro propanol (TFP) has been extensively applied in the manufacture of CD-R and DVD-R, due to its ability to dissolve organic dyes. The spin coating process produces a large amount of wastewater containing TFP. No reports have been written on the biodegradability of TFP to the authors¡¦ knowledge. Additionally, HMDS (hexamethyldisilazane) has been extensively used in life science microscopy and material science. For instance, the semiconductor industry employs HMDS to promote the adhesion of photo-resistant material to oxide(s). HMDS is classified as a carcinogen, and has an ammonia odor. Condensing incinerators have been found to be unsuitable for treating HMDS-containing waste gases, because of the formation of silicon dioxide, which blocks porous adsorbents. Biological treatment also appears to be unpromising due to its low water solubility and limited biodegradability. This investigation evaluates the feasibility, effectiveness and oxidation characteristics of aqueous DMSO, TFP and gaseous HMDS (hexamethyldisilazane) by UV/O3 processes. A reactor made entirely of acrylic plastic with an effective volume of 10 L was employed for the reactions. The tested VOCs concentrations were adjusted to 400¡V890mg/L and 772¡V887 mg/L for DMSO and TFP, respectively, and the gas (ozone-enriched air) flow rate was controlled at 3L/min. The effects of various solution pH values (acidic, alkaline, uncontrolled), solution temperatures (26 oC, 37 oC, 48 oC and 60 oC), and UV wavelengths (254 nm and 185+254 nm) on the removal of tested VOCs were studied . Additionally, the operation costs of treating DMSO and TFP by UV/O3 were estimated. Experimental results demonstrate that acidic conditions (pH = 3.6) favored the degradation of DMSO, and that the removal efficiency could reach 95% at a volumetric UV intensity P/V of 2.25 W/L and a reaction time of 120 min. However, alkaline conditions (pH = 9.5) favored the decomposition of TFP, with the removal efficiency reaching 95% at P/V = 2.5 W/L and a reaction time of 60 min. Both DMSO and TFP exhibited zero-order degradation kinetics when sufficient ozone was supplied. Raising the oxidation temperature did not increase the UV/O3 oxidation of TFP in the tested concentration and temperature ranges. Operation costs of the UV/O3 per unit volume of wastewater with DMSO or TFP are comparable to those of the methods described in the literature. For the gaseous HMDS oxidation, two batch reactors with effective volumes of 1.2 and 5.8 L were used employed with the decomposition occurred under UV (185+254 nm) irradiation and UV (254 nm)/O3 processes. Tests were performed with initial HMDS concentrations of 32¡V41mg/m3 under various initial ozone dosages (O3 (mg)/HMDS (mg) =1¡V5), atmospheres (N2, O2, and air), temperatures (28 oC, 46 oC, 65 oC and 80 oC), relative humilities (20%, 50%, 65% and 99%) and volumetric UV power inputs (0.87 W/L, 1.74 W/L, 4.07 W/L and 8.16 W/L) to assess their effects on the HMDS degradation rate. Results of this study demonstrate that the decomposition rates for the UV (185+254 nm) irradiation exceeded those for the UV (254 nm)/O3 process for all conditions. UV (185+254 nm) decompositions of HMDS displayed apparent first-order kinetics. A process with irradiation of UV (185+254 nm) to HMDS in air saturated with water at temperatures of 46¡V80 oC favors the HMDS degradation. With the above conditions and a P/V of around 8 W/L, k≈ 0.20 s−1, and over 90% of the initial HMDS was degraded in a time of 12s. The main mechanisms for the HMDS in wet air streams irradiated with UV (185+254 nm) were found to be caused by OH free radical oxidation produced from photolysis of water or O (1D) produced from photolysis of oxygen. Economic evaluation factors of UV (185+254 nm) and UV (254 nm)/O3 processes at various UV power inputs were also estimated.

In this thesis, a detailed investigation has been carried out on the use of electro-Fenton technique for the oxidation of the some persistent organic pollutants for the sake of water remediation. This technique produces *OH radicals electrocatalytically and uses them to oxidize the organic pollutants. The overall study can be divided into three parts. In the first part, the removal of selected synthetic dyes and pesticides from water was investigated by using carbon felt (CF) cathode. The oxidation kinetics of the synthetic dyes (Acid Orange 7 and Basic Blue 3) and pesticides (picloram, propham, azinphos-methyl and clopyralid) were determined. Mineralization kinetics of the related organic pollutants in aqueous medium was followed by total organic carbon and chemical oxygen demand analysis. The overall mineralization was obtained in all cases. Identification and quantification of the oxidation by-products of the given synthetic dyes and pesticides were performed by high performance liquid chromatography, gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry and ion chromatography. These systematic analysis showed that the initial organic pollutants were converted into three intermediate forms; organic intermediates, short-chain aliphatic carboxylic acids and inorganic ions. Based on the intermediates identified, a plausible mineralization pathway was proposed for each dye and pesticide.In the second part of the study, the H2O2 production ability of carbon sponge (CS) as a novel cathode material for the electro-Fenton technique was investigated for the first time in the literature. The obtained results indicated that CS has a H2O2 production ability three times higher than the classical cathode CF.In the third and last part, the efficiency of boron doped diamond (BDD) as an anode in the electro-Fenton technique was investigated. Firstly, the oxidation and mineralization ability of BDD was tested for herbicide propham in anodic oxidation conditions. Then, the combination of CS and BDD electrode in the electro-Fenton technique was examined. The obtained results indicated that this combination allowed the most efficient results throughout the thesis. Moreover, the use of BDD anode in the electro-Fenton technique had considerable effect on the oxidation and mineralization of organics and especially carboxylic acids such as oxalic and oxamic acids which were highly resistant to mineralization in the case of Pt anode

De nombreuses molécules médicamenteuses ne sont pas traitées efficacement par les techniques classiques utilisées dans les stations d'épuration et s’accumulent dans les milieux naturels. L’objectif de cette thèse a été de développer un procédé d’oxydation avancée utilisant un plasma non thermique généré par décharge électrique pour le traitement de molécules médicamenteuses et d’identifier le schéma de dégradation d’une des molécules d’étude, à savoir le paracétamol. Les traitements ont été réalisés à l’aide de deux réacteurs : un réacteur multi-pointes avec le plasma au contact direct du liquide à traiter et un réacteur fil-cylindre avec le plasma en amont du liquide à traiter. Des taux de conversion supérieurs à 80% ont pu être obtenus avec des rendements énergétiques, qui peuvent atteindre 8g/kWh et 39 g/kWh pour le paracétamol et l’ésoméprazole, respectivement. La décharge électrique créée entre une pointe et le liquide a été caractérisée par la spectroscopie d’émission optique afin d’observer la présence des espèces oxydantes produites par le plasma et d’estimer la température du milieu faiblement ionisé. Les espèces produites dans le liquide lors de la dégradation du paracétamol et de l’ésoméprazole qui ont été identifiées par la technique HRMS, entre autres, sont principalement des acides carboxyliques ainsi que des produits azotés. L’identification des voies de production pour la formation des principaux produits ont été étudiés particulièrement à l’aide de nombreuses méthodes chimiques comme HPLC/MS, MS/MS, et de différents marquages de paracétamol. Il a été prouvé que les principaux acides carboxyliques produits proviennent de la rupture du cycle aromatique. En conclusion, cette étude nous a permis d’obtenir des rendements énergétiques de traitement des deux molécules d’étude comparables à ceux retrouvés en littérature, et surtout d’établir un chemin de dégradation du paracétamol. / Many drug molecules are not effectively treated by conventional techniques used in wastewater treatment plants and accumulate in natural environments. The objective of this thesis was to develop an advanced oxidation process using a non-thermal plasma generated by electric discharge for the treatment of drug molecules (paracetamol and esomeprazole). The NTP treatments were carried out using two reactors: a multiple needle-to-plate reactor with the plasma in direct contact with the liquid to be treated and a wire-cylinder reactor with the plasma up stream of the liquid to be treated. Conversion rates higher than 80% have been obtained with energy yields, which can reach 8 g/kWh and 39 g/kWh for paracetamol and esomeprazole, respectively. The electrical discharge created between the need leand the liquid has been characterized by optical emission spectroscopy to observe the presence of the oxidative species produced by the plasma and to estimate the temperature of the ionized medium. The species produced in the liquid during the degradation of paracetamol and esomeprazole have been identified by the HRMS technique. The produced species, are mainly carboxylic acids as well as nitrogen products. The identification of production pathways for the formation of the main products has been studied particularly using numerous chemical methods such as HPLC/MS, MS/MS, and different labelling of paracetamol. It has been proven that the main carboxylic acids produced come from the breaking of the aromatic ring. In conclusion, this study allowed us to obtain energy efficiencies of treatment of the two study molecules comparable to those found in literature, and especially to establish a pathways of degradation of paracetamol.

Made available in DSpace on 2015-05-14T13:21:37Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1224120 bytes, checksum: f64c0391dc1efdba15b19e77bab0b144 (MD5) Previous issue date: 2014-05-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Given the growing trend to explore biofuels as a renewable energy source with less environmental impact and considering thatthe transesterification by basic catalysis is the most used in the biodiesel purification, it becomes importantperform treatments order to reuse of wash water biodiesel. In this sense, the objective of this study was to apply and compare photolysis (UV) followed by advanced oxidation treatment; UV/H2O2; Fenton (Fe2+/H2O2) and photo-Fenton (Fe2+/UV/H2O2)as well as perform toxicity tests using seeds lettuce (Lactuca sativa) before and after treatment of effluents.washing water was collected in biodiesel industry located in Caetés - PE. Biodiesel obtained from cotton oil was washed sequentially with two portions of one hundred liters of water. It was found pH values of 3.8 and 3.4; The minimum turbidity of 158 NTU and a maximum of 7.369 and EC was 0.25 and 0.86, minimum of 160,000 and maximum of 184.000 mg.L-1 COD, BOD ranging 830 and 2,150 mg.L-1 and the content of oils and greases varied 2,852 and 21,761 mg.L-1, respectively for first and second washing water. After application of photolysis process, reduction occurred (82.6% and 72.5%) for the water turbidity resulting from two washes.For the first rinse water, UV/H2O treatment resulted in a reduction of turbidity (91.4%) and COD (70.4%). For water resulting from second wash, reduced turbidity (84%) and in COD (80%), determined by photo-Fenton process. Through toxicity tests using lettuce seeds, it was proven that the best IG% occurred in treatments photolysis (95.3%) and UV/H2O2 (92.8%) / Diante da crescente tendência de se explorar os biocombustíveis como a fonte de energia renovável e com menor impacto ambiental e considerando que a transesterificação pela catálise básica é a mais utilizada na purificação do biodiesel, torna-se relevante realizar tratamentos visando à reutilização da água de lavagem do biodiesel. Neste sentido, o objetivo deste trabalho foi aplicar e comparar aFotólise (UV)seguidados tratamentos oxidativos avançados; UV/H2O2; Fenton (Fe2+/H2O2) e foto-Fenton (Fe2+/UV/H2O2), bem como realizar ensaios de toxicidade usando sementes de alface (lactuca sativa), antes e após o tratamento dos efluentes. A água de lavagem foi coletada na usina de biodiesel localizada na cidade de Caetés PE. O biodiesel obtido a partir do óleo de algodão foi lavado, sequencialmente, com duas porções de cem litros de água. Foram encontrados valores de pH de 3,8 e 3,4; a turbidez apresentou valor mínimo de 158 e máximo de 7369 UNT; a CE foi de 0,25 e 0,86; o valor mínimo de 160.000 e máximo de 184.000 mg.L-1de DQO; a DBO variou de 830 a 2.150 mg.L-1 e o teor de óleos e graxas oscilaram de 2.852 a 21.761 mg.L-1, respectivamente, para água de primeira e segunda lavagem. Após a aplicação do processo por fotólise, ocorreu redução (82,6% e 72,5%) da turbidez para as águas resultantes das duaslavagens. Para a água da primeira lavagem, o tratamento por UV/H2O2 resultou na melhor redução da turbidez (91,4%) e DQO (70,4%). Para a água resultante da segunda lavagem a turbidez reduziu em (84%) e a DQO em (80%), determinadas pelo processo de foto-Fenton.Através dos testes de toxicidade utilizando sementes de alface, ficou comprovado que o melhor IG% ocorreu nos tratamentos por fotólise (95,3%) e UV/H2O2 (92,8%)

Orientadores: José Roberto Guimarães, Carlos Gomes da Nave Mendes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo / Made available in DSpace on 2018-08-18T03:12:06Z (GMT). No. of bitstreams: 1 Gasparini_MirthysCozzett_M.pdf: 1574617 bytes, checksum: 879f212f74e005fca5974d6f943a790e (MD5) Previous issue date: 2011 / Resumo: No presente trabalho foi realizada a caracterização de várias correntes de águas de processo da REPLAN (Refinaria de Paulínia), bem como a avaliação dos processos de fotólise (UV), peroxidação (H2O2), peroxidação assistida por radiação ultravioleta (H2O2/UV), reagente de Fenton (H2O2/Fe2+) e foto-Fenton (H2O2/Fe2+/UV) no tratamento de um dos efluentes, principalmente na degradação dos compostos orgânicos. Analisando-se os dados de caracterização dos diferentes efluentes foi possível sugerir alternativas de reuso no processo de refino, como também selecionar a corrente de água ácida retificada para aplicação dos processos físico-químicos de tratamento. A eficiência dos ensaios de tratabilidade foi baseada na redução da concentração do carbono orgânico dissolvido (COD). Dentre os processos estudados, os processos oxidativos avançados (POA) H2O2/UV e foto-Fenton apresentaram 95 % de eficiência após 150 minutos de ensaio. As condições ótimas foram obtidas na relação mássica COD: H2O2 de 1:7 para o processo peroxidação assistida por radiação UV, e de 1:5 e concentração de Fe2+ de 31 mg/L para o processo foto-Fenton. O efluente tratado pelo processo H2O2/UV poderia ser reutilizado como água de reposição no sistema de resfriamento, já que esta é responsável por 49 % do total de água utilizada na refinaria / Abstract: In the present study was performed the characterization of various process water from REPLAN (Paulínia Refinery) as well as an assessment of 5 processes to treat one of the effluents: photolysis (UV), peroxidation (H2O2), peroxidation assisted by ultraviolet radiation (H2O2/UV), Fenton reagent (H2O2/Fe2+) and photo-Fenton (H2O2/Fe2+/UV), in order to degrade the organic compounds. Effluents characterization results provided reuse possibilities in the process refining and also selected the stripped sour water stream for application of physical-chemical treatments. The processes efficiency was evaluated by the dissolved organic carbon (DOC) reduction. Among the processes studied, the advanced oxidation processes (AOPs) H2O2/UV and photo-Fenton reached 95 % efficiency after 150 minutes of reaction. The optimum conditions were obtained in a mass ratio COD: H2O2 of 1:7 for peroxidation assisted by UV radiation, and of 1:5 with 31 mg/L of Fe2+ for photo-Fenton. The effluent treated by AOP H2O2/UV could be reused as make-up water in cooling systems, since it is responsible for 49 % of the total water used in the refinery / Mestrado / Saneamento e Ambiente / Mestre em Engenharia Civil

A degradação do herbicida Diuron comercial (Nortox SA) foi realizada utilizando os ânodos Ti/RuxTi(1-x)O2 e Ti/IrxTi(1-x)O2 (x = 0,3; 0,5 e 0,7). A investigação da degradação foi conduzida na presença e na ausência de cloreto. O estudo da remoção do herbicida em função da densidade de corrente na ausência de cloreto rendeu remoções de 41 e 49% de demanda química de oxigênio (DQO) e remoções de 10 e 14% de carbono orgânico total (COT) a 100 mA cm-2, respectivamente. Mantendo-se o tempo de eletrólise constante (4 h), a composição do ânodo Ti/Ru0,7Ti0,3O2 foi determinada como a mais ativa para remoção do Diuron e seus subprodutos. Com a adição de cloreto, a taxa de degradação dobrou, e obteve-se 100% de remoção de DQO para o ânodo Ti/Ru0,3Ti0,7O2. O herbicida Alaclor foi totalmente mineralizado por diferentes processos eletroquímicos oxidativos avançados (PEOAs), empregando célula eletroquímica em escala de bancada (100 mL) equipada com cátodo de difusão de ar capaz de eletrogerar H2O2 e ânodos de Pt e diamante dopado com boro (BDD). O melhor desempenho para o tratamento de 100 mL de solução Alaclor 0,60 mmol L-1 durante 360 min, foi obtido por meio do processo fotoeletro-Fenton (FEF) empregando ânodo de BDD na presença de 0,5 mmol L-1 de Fe2+. De acordo com as análises de CG-MS, a etapa de degradação do Alaclor envolveu quatro vias diferentes de reação (desalquilação, ciclização, cisão da ligação R-N e hidroxilação), resultando em nove subprodutos que, em seguida, levaram ao surgimento de ácidos carboxílicos que foram detectados. Diferentes quantidades de íons nitrogenados (NH4+ e NO3-) e clorados (Cl-, ClO3- e ClO4-) foram acumulados nas soluções finais da degradação, dependendo do ânodo e da corrente aplicada. O herbicida Diuron (0,185 mmol L-1 e pH 3,0), foi tratado também por diferentes PEOAs, como oxidação anódica com H2O2 eletrogerado (OA-H2O2), eletro-Fenton (EF) e fotoeletro-Fenton empregando luz UVA (FEF) ou FEF empregando luz solar (FEFS). Os ensaios foram realizados em uma célula eletroquímica em escala de bancada (100 mL) e em seguida testes em uma planta pré-piloto (2,5 L). Nos experimentos com célula eletroquímica em escala de bancada, o tratamento FEF empregando ânodo de BDD foi o método mais potente, produzindo 93% de mineralização após 360 min a 100 mA cm-2. Na planta de fluxo pré-piloto, o processo FEFS atingiu uma porcentagem de mineralização máxima de 70% a 100 mA cm-2. Os ácidos oxálico e oxâmico foram detectados como os ácidos carboxílicos finais e íons amônio e cloreto também foram encontrados, onde o último íon foi parcialmente convertido em íons clorato e perclorato na superfície do ânodo de BDD / Commercial herbicide Diuron solution (Nortox SA) was degrated using Ti/RuxTi(1-x)O2 and Ti/IrxTi(1-x)O2 (x = 0.3, 0.5, and 0.7) anodes. Degradation was investigated in the presence and in the absence of chloride. In the absence of chloride, herbicide removal yielded 41 and 49% COD (chemical oxygen demand) removal, and 10 and 14% TOC (total organic carbon) removal at 100 mA cm-2, respectively. For a constant electrolysis time (4 h), Ti/Ru0.7Ti0.3O2 anode composition removed Diuron and its byproduct the most activelly. Addition of chloride doubled the removal ratio, and the Ti/Ru0.3Ti0.7O2 anode afforded 100% COD removal. Electrochemical advanced oxidation processes (EAOPs) quickly degraded and even totally mineralized the herbicide Alachlor in electrochemical cells equipped with a carbonaceous air-diffusion cathode that was able to electrogenerate H2O2 and with a Pt or boron-doped diamond (BDD) anode. The photoelectron-Fenton (PEF) process with BDD in the presence of 0.5 mmol L-1 Fe2+ performed the best in Alachlor solutions treatment (100 mL, 0.60 mmol L-1, 360 min.). According to GC-MS analyses, Alachlor degradation involved four different reaction pathways (dealkylation, cyclization, R-N bond cleavage and hydroxylation), to give nine byproducts, including the detected carboxylic. Different amounts of nitrogenated (NH4+ and NO3-) and chlorinated (Cl-, ClO3- and ClO4-) ions accumulated in the final solutions depending on the anode and the applied current. The herbicide Diuron (0.185 mmol L-1 and pH 3.0) was treated using different EAOPs like anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF), and solar PEF (SPEF). Experiments were performed in 100 mL electrochemical cells, and in a 2.5 L pre-pilot flow plant. In the electrochemical cells, the PEF treatment with BDD was the most potent, yielding 93% mineralization after 360 min at 100 mA cm-2. In the pre-pilot flow plant, the SPEF process furnished maximum mineralization of 70% at 100 mA cm-2. Oxalic and oxamic acids were detected as final carboxylic acids. Ammonium and chloride ions were also released; the latter ion was partially converted into chlorate and perchlorate ions at the BDD surface

Orientador: Wilson de Figueiredo Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-24T02:49:05Z (GMT). No. of bitstreams: 1 Torres_CarolinaFerreira_M.pdf: 3163293 bytes, checksum: 169b47e5a4d52ba3e29d4ad8c88bec54 (MD5) Previous issue date: 2013 / Resumo: O uso de fotocatalisadores suportados tem sido a estratégia preferencial em fotocatálise heterogênea, uma vez que a separação do material fotoativo do meio reacional é difícil e dispendiosa. A quitosana é um biopolímero de disponibilidade ilimitada, fonte renovável, é biodegradável e possui alto poder de adsorção. Esferas de quitosana impregnadas com TiO2 P-25 foram obtidas pela técnica de coagulação, onde uma mistura de quitosana e TiO2 P-25 é dissolvida em meio ácido e gotejada sobre um banho alcalino formando as esferas. Depois de lavadas e secas estas foram caracterizadas quanto à sua morfologia, resistência à solução ácida e à fotodegradação, área superficial, DRX, refletância de radiação UV/Vis e absorção de radiação IV. A atividade fotocatalítica das esferas foi avaliada utilizando solução de ácido salicílico 50 mg L. Placas de Petri contendo 0,5 g de esferas com relação quitosana: TiO2 P-25 na proporção de 1:10 (m/m) e 25 mL de solução de AS foram iluminadas por radiação UV e em intervalos de 8 horas alcançou-se mineralização de 40%, determinado por medidas de COT e emissão de fluorescência. As esferas foram reutilizadas em mais dois ciclos de ensaios de fotodegradação sem que passassem por qualquer processo de limpeza e sem perderem sua atividade fotocatalítica. / Abstract: The use of supported photocatalysts has been the preferred strategy for heterogeneous photocatalysis, since the separation of photoactive material from the reactional mean is difficult and expensive. Chitosan is a biopolymer of unlimited availability; it is a renewable source, biodegradable and has a high adsorption power. Chitosan beads impregnated with TiO2 P-25 were obtained by the coagulation technique, where a mixture of chitosan and TiO2 P-25 is dissolved in an acidic mean and dripped onto an alkaline bath, forming the spheres. Once washed and dried, they were characterized as to their morphology and resistance to acid solutions and photodegradation, as well as to their surface area, XRD, UV/Vis radiation reflectance and IR radiation absorption. The photocatalytic activity of the spheres was evaluated using salicylic acid solution 50 mg L. Petri dishes containing 0.5 g of beads with chitosan proportion: TiO2 P-25 at a ratio of 1:10 (w/w) and 25 mL of SA solution were illuminated by UV radiation and within 8-hour intervals a mineralization of 40% was reached, as determined by TOC measures and fluorescence emission. The beads were reused in two other test cycles of photodegradation without undergoing any cleaning process and without losing its photocatalytic activity. / Mestrado / Quimica Analitica / Mestra em Química

Orientador: Peterson Bueno de Moraes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia / Made available in DSpace on 2018-08-21T23:07:04Z (GMT). No. of bitstreams: 1 Silveira_JeffersonEduardo_M.pdf: 1833335 bytes, checksum: 71226fb620b38ed3dd8fd9ee6cfac08d (MD5) Previous issue date: 2012 / Resumo: A crescente degradação dos corpos d'água é assunto de constante interesse dos pesquisadores, da opinião pública e da mídia, devido à preocupação com a saúde pública, com os meios de produção e no legado às gerações futuras. Embora nos últimos anos as engenharias química, sanitária e ambiental tenham tido um significativo avanço nos métodos para tratamento de resíduos, alguns tipos de efluentes de composição complexa, como o lixiviado de aterro sanitário, não são adequadamente tratados pelos processos convencionais. Neste trabalho, propôs-se o uso da tecnologia eletroquímica, já utilizada na remedição de diversos tipos de resíduos e efluentes, para o desenvolvimento e aperfeiçoamento de um reator eletroquímico, em escala piloto, para tratamento do lixiviado do aterro sanitário do município de Limeira-SP. O lixiviado de aterro sanitário é um líquido escuro, com potencial patogênico, toxicológico e que pode conter compostos orgânicos como fenóis, pesticidas e íons metálicos. Foi utilizado um reator eletroquímico com eletrodos de titânio recobertos com 70%TiO2/30%RuO2 operando em batelada com recirculação, visando à redução da cor, carga orgânica e toxicidade. A partir dos resultados dos parâmetros físico-químico e biológicos, o sistema foi otimizado quanto à vazão, densidade de corrente, concentração de eletrólitos suporte e tempo de tratamento. Após 60 minutos de tratamento em densidade de corrente de 250 mA cm-2, concentração de eletrólito de 0,5 M de NaCl e vazão de 400 L h-1 foi possível remover 80% de DQO, 75% de N-NH3, 65% de COT e 90% de DBO. Levando-se em conta somente a remoção de amônia, a densidade de corrente mínima de 25 mA cm-2 já teve excelente desempenho após 30 minutos de tratamento. O sistema pode ser considerado economicamente viável para tratar este tipo de efluente em comparação aos tratamentos convencionais normalmente utilizados, com a vantagem de ser rápido, ocupar pouco espaço e não gerar lodo / Abstract: The increase in deterioration in the quality of water bodies is a subject of interest for researchers, public and media due to concern about public health. Although chemical engineering and environmental sciences have been experiencing lately significative advance in methods for wastewaters treatment, some types of effluents with complex composition such as landfill leachate are not adequately treated by conventional processes. In this work, we proposed the use of electrochemical technology, already used in the remediation of several types of waste and effluents, for development and improvement of an electrochemical pilot scale flow reactor for the treatment of raw landfill leachate from Limeira city, SP. The landfill leachate is a dark liquid with toxicological and pathogenic potential and may contain organic compounds such as phenols, pesticides and metallic ions. We used an electrochemical reactor with titanium oxide electrodes coated with 70% TiO2/30% RuO2 operating in batch recirculation mode, aiming to reduce color, organic load and toxicity. The electrochemical system was optimized from physicochemical and biological analyses considering the flow rate, current density, supporting electrolyte concentration and treatment time. Tests in 60 minutes at 250 mA cm-2, NaCl 0.5 M and flow rate of 400 L h-1 resulted on 80% COD, 75% NH3 - N, 65% TOC and 90% of BOD removal. Considering solely the removal of ammonia, 25 mA cm-2 was sufficed to reach a good performance in 30 minutes of treatment. The system showed be economically interesting for the treatment of this type of effluent when compared to conventional treatments normally used, because have the following advantages: higher degradation rates, small footprint, zero or low-generation of sludge / Mestrado / Tecnologia e Inovação / Mestre em Tecnologia

Recently, an increasing problem in wastewater treatment is the insufficient removal of organic pollutants. These substances can be toxic to the environment already in a small amount, either acutely or chronically. The goal is therefore to develop of technologies that ensure their effective removal. One possibility is to use advanced oxidation processes. Advanced oxidation processes work on the principle of non-selective oxidation mediated by OH radicals. Several methods such as O3/H2O2 (Peroxone), UV/H2O2 or Fenton´s reaction can be used to generate them. The aim of this thesis was to evaluate the effectiveness of the used advanced oxidation processes in wastewater treatment via ekotoxicity tests. Wastewater samples treated with advanced oxidation processes on the pilot unit showed low values of acute toxicity for selected test organisms (D. magna, T. platyurus, S. alba, L. minor). For the sample of waste water that was treated with the UV/H2O2 on AOP laboratory unit, there was an increase in acute toxicity on the testing organism D. magna and L. minor. The similar effect was observer in the tests with the D. magna with the model samples treated with the same method, while the tests on the L. minor showed a reduction in toxicity.

This thesis deals with advanced oxidation processes (AOPs) and it’s use for removal of micropollutants from wastewater. The first chapter explains the need AOPs, water quality, pollution and substances that are present in the water. Further, the first chapter outlines approach of the current legislation to micropollutants. The second chapter explains the theory and principle of operation of AOPs. This chapter is divided into two sections. The first section describes AOPs, which were tested at selected WWTP. In the second section, there are described some other AOPs. The third chapter is a literature retrieval of AOPs dealing with the removal of micropollutants. This chapter is focused on the removal of hormones by AOPs using ozone-based AOPs. The fourth chapter describes the actual testing of selected AOPs. The chapter describes selected WWTP, pilot-scale AOP unit and test results. In the last chapter there is designed and described full-scale AOP tertiary unit for removing of micropollutants. The last chapter also contains economic analysis of the proposed tertiary unit.