Made available in DSpace on 2014-12-17T15:01:21Z (GMT). No. of bitstreams: 1 SyllosSS_DISSERT.pdf: 3274284 bytes, checksum: efc9ef709dfd1e06b4170ed41eedf3fb (MD5) Previous issue date: 2010-02-22 / The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitable surfactant was the EO 7 due to the lower reagent onsumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min / A gera??o de res?duos na maioria dos processos industriais ? quase que inevit?vel. Na ind?stria do petr?leo, um dos grandes vil?es para o meio ambiente ? o enorme volume de ?guas produzidas nos campos de petr?leo. Este efluente apresenta composi??o complexa e aliado ao grande volume envolvido pode-se tornar bastante danoso ao meio ambiente quando descartado de forma inadequada. Esta pesquisa est? centrada na an?lise das efici?ncias dos processos de flota??o em coluna e oxida??o avan?ada por processo foto-Fenton para remo??o/degrada??o de org?nicos presentes na ?gua produzida. Uma s?rie de tensoativos derivados de ?lcool laur?lico foi utilizada na flota??o para promover a melhoria da cin?tica e efici?ncia de separa??o. Os experimentos foram realizados com efluente sint?tico contendo xileno como poluente modelo. Os dados experimentais obtidos da flota??o apresentaram cin?tica de 1? ordem, identificada pela qualidade dos ajustes lineares. As melhores condi??es encontradas foram 0,029 g.L-1 para o EO 7, 0,05 g.L-1 para o EO 8, 0,07 g.L-1 para o EO 9, 0,045 g.L-1 para o EO 10 e 0,08 g.L-1 para o EO 23 com as seguintes constantes de velocidade iguais a 0,1765, 0,1325, 0,1210, 0,1531, 0,1699 min-1, respectivamente. Para a s?rie estudada, o tensoativo mais adequado foi o EO 7 devido o menor consumo de reagente, maior constante cin?tica de separa??o e maior efici?ncia de remo??o do xileno da fase aquosa (98%). De forma similar a flota??o, o processo foto-Fenton demonstrou ser eficiente para degrada??o do xileno alcan?ando efici?ncia de mineraliza??o da carga org?nica entre 90% e 100% em 90 min

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

Durante o processo metalúrgico de usinagem de uma peça ocorre a geração de calor proveniente do atrito ferramenta/peça e cavaco/ferramenta. Para que ocorra uma menor geração de calor possibilitando o manuseio, bem como a minimização na deformação da peça, utilizam-se fluidos, que são soluções lubrificantes à base de óleos, água ou polímeros, podendo ser sintéticos ou não, diminuindo, assim, o coeficiente de atrito reduzindo-se a quantidade de calor gerado no processo. Há uma grande variedade de fluidos de corte disponíveis no mercado que são constituídos por diversos compostos como: aminas, compostos clorados e/ou aromáticos, glicóis, nitrosaminas além da presença de metais provenientes do processo de manufatura, portanto, sem tratamento, não podem ser lançados na rede de esgoto convencional. Atualmente não há um método de tratamento para os fluidos de corte nas indústrias. Nesse contexto, propõe-se um estudo sobre a viabilidade dos tipos de tratamento dos fluidos de corte para uma disposição adequada. Os processos de tratamento propostos neste trabalho compreendem hidrolise ácida e Processo Oxidativo Avançado (POA), mais especificamente, Sistema Fenton, além de propor um tratamento baseado na fotodegradação. A caracterização do fluido antes e após seu tratamento foi realizada por técnicas analíticas e espectrométricas. Os processos oxidativos mostraram-se satisfatórios para o tratamento dos efluentes, reduzindo os níveis de contaminantes aos permitidos pela legislação. O processo foto-Fenton mostrou-se mais eficiente que o processo Fenton na degradação de todos os parâmetros avaliados, incluindo BTEX e HPAs. Os processos de hidrólise ácida não apresentaram resultados satisfatórios, reduzindo apenas os metais aos níveis permitidos para descarte. / During the cutting process, part of the heat generation results from tool-part and chip-tool friction. So that it happens a smaller generation of heat making possible the handling, as well as minimization in the tool deformation, cutting fluids are used, that are the oils base, water or polymeric lubricating solutions, could be synthetic or no, decreasing the attrition coefficient being reduced the amount of heat generated in the process. There is a great variety of cutting fluids that are constituted for several composed as: amines, chlorinated and/or aromatic composed, glycols and nitrosamines besides the presence of metals proceeding of manufacture process, therefore, without a treatment, they cannot be discarded in the conventional sewerage system. At the moment there isn\'t a treatment method for the cut fluids in the industries. In that context, intends a study about the viability types of cutting fluids treatment for appropriate disposition. Treatment processes proposed in this work understand acid hydrolysis and Advanced Oxidative Process (AOP), more specifically, Fenton System, in addition proposing a treatment based on the photodegradation (photo-Fenton process). The characterization of fluid before and after treatment it was accomplished by analytical and spectrometry techniques. Oxidative processes were exposed satisfactory for cutting fluids treatment, reducing the levels of pollutants to the allowed by the legislation. Photo-Fenton process was shown more efficient than Fenton process in the oxidation of BTEX and PAHs. Acid hydrolysis processes didn\'t present satisfactory results, just reducing the metals at the levels allowed for discard.

Philosophiae Doctor - PhD / Emerging micropollutants such as bisphenol-A and 2-nitrophenol present a great threat in drinking water due to their adverse effects. Most conventional technologies in water and wastewater treatment are not designed to eliminate these xenobiotics; instead pollutants are merely transferred from one phase to another. Advanced oxidation technologies (AOTs) however, have been identified as suitable routes for the degradation of these potential damaging substances based on free radical mechanisms and use of less expensive chemicals. Moreover, due to the structural complexity of wastewater and the existence of pollutants as mixtures, no single advanced oxidation technology can convincingly remove all forms of contaminants and then most often than not, a combination of treatment processes is required for an effective purification process. Besides, the problem of adequate degradation of emerging contaminants in the environment, when AOT(s) are used individually, they present inherent problems. For instance, powder TiO₂ photocatalysts obstruct light penetration, thus prevent effective interaction of UV light with the target pollutants, and particulates present problems of post-filtration and recovery of catalyst particles after treatment. Additionally, TiO₂ has a high band gap energy, high electron-hole recombination rate, and is prone to aggregation of the suspended particles. Similarly, the dielectric barrier discharge (DBD) system produces ultra violet light and hydrogen peroxide within the plasma zone which is not fully maximised for the mineralization of persistent organic pollutants. Rapid oxidation and aggregation of nano zero valent iron particles in photo-Fentons process reduce the particles mobility and affect its performance. In the same vein, the jet loop reactor (JLR) system is characterised by low impingement yield, which is responsible for low mineralization rate. In light of this background, this research investigated the degradation of bisphenol-A and 2- nitrophenol in aqueous solution using the following combined advanced oxidation methods: DBD/supported TiO₂ or Ag doped TiO₂ photocatalysts, DBD/photo-Fenton induced process and JLR/UV/H₂O₂. The target was to assess the performance of each single system and then identify the best combined AOTs capable of significantly mineralizing the target compounds. Firstly, two materials were developed namely supported TiO₂ and stabilized nano zero valent Fe. The TiO₂ photocatalyst supported on a stainless steel mesh was synthesised using sol-gel solution of 8 % PAN/DMF/TiCl₄. The influence of calcination temperature and holding time on the formation of nanocrystals was investigated. Afterwards, various amounts of metallic silver were deposited on the (optimum) supported TiO₂ photocatalyst using thermal evaporation. The catalysts were characterized by several analytical methods; HRSEM, HRTEM, EDS, SAED, FTIR, TGA-DSC, UV-vis/diffuse reflectance spectroscopy, XRD, BET, and XPS. The photocatalytic activity of the prepared catalysts was determined using methylene blue as a model pollutant under ultra-violet light irradiation. Secondly, the TiO2 photocatalyst and 2.4 % Ag doped TiO₂ nanocomposites obtained as optimums (in section 1) were combined with the DBD to decompose BPA or 2-NP in aqueous solution. Moreover, the photo-Fenton process was applied for degradation of the model pollutants, and different dosages of stabilized nZVI (in the range of 0.02 -1.00 g) were added to the DBD system to induce the photo-Fenton process and improve BPA or 2-NP degradation efficiency. Finally, a jet loop reactor (JLR) presenting advanced mixing by the “impinging effect” was explored to decompose BPA or 2-NP in aqueous solution as a function of inlet applied pressure, solution pH, and initial concentration of BPA or 2-NP. Subsequently, different concentrations of hydrogen peroxide (H₂O₂) were added to the JLR to enhance the mineralization process. Furthermore, a combination of JLR with in-line UV light and H₂O₂ were further utilised to decompose BPA or 2-NP in aqueous solution. The residual concentration of the model compounds and intermediates were analysed using high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LCMS). The concentration of the ozone, hydrogen peroxide and hydroxyl radicals generated by the DBD in the presence or absence of a catalyst was monitored using Ultraviolet-visible spectroscopy and Photoluminescence spectroscopy. The results revealed that the optimal thermal conditions to obtain well supported uniformly grown, highly active crystalline TiO₂ catalysts with high specific surface area was 350 ºC at a 3 h holding time in N2 atmosphere with a flow rate of 20 mL/min. Pyrolysis temperature and holding time played an important role on the crystalline nature and photocatalytic activity of the catalyst. Moreover, 2.4 % Ag doped TiO₂ nanocomposites exhibited higher photocatalytic activity for methylene blue degradation than the undoped supported TiO₂ nanocrystals. The results indicated that combining DBD with 2.4 % Ag doped TiO₂ nanocomposites achieved 89 % and 81 % removal efficiency for BPA or 2-NP compared to 67.22 % or 56.8 % obtain when using the DBD system alone. The 2.4 % Ag doped TiO₂ nanocomposites demonstrated excellent activity and offered photochemical stability after four repeated applications.In the case of the photo-Fenton induced process, nano zero valent iron particles (nZVI) stabilized with polyethylene glycol were synthesised using a modified borohydride reduction method. The HRSEM, BET, XRD, and XPS analysis confirmed the formation of filamentous, high surface area iron nanoparticles in the zero valent state. Unlike combined DBD/Ag doped TiO2 nanocomposites, 100 % or complete removal of BPA or 2-NP in aqueous solution was achieved with DBD/nZVI system within 30 minutes compared to 67.9 % (BPA) or 56.8 % (2-NP) with DBD alone after 80 minutes. The removal efficiency was attributable to the production of an increased concentration of OH radicals as well as existence of a synergetic effect in the combined DBD/nZVI system. Five new transformation products namely: 4-nitrophenol (C₆H₅NO₃), 4-nitrosophenolate (C₆H₄NO₂), 4-(prop-1-en-2-yl) cyclohexa-3,5-diene-1,2-dione, (C₉H₈O₂), 4-(2- hydroxylpropan-2-yl)cyclohexane-3,5-diene-1,2-dione (C₉H₁₀O₃), and 1,2-dimethyl-4-(2- nitropropan-2-yl)benzene (C₉H₁₀NO₄) were identified during the degradation of BPA. While, three aromatic intermediate compounds such as 2-nitro-1,3,5-benzenetriolate (C₆H₂NO₅), 2- nitro-1,4-benzoquinone (C₆H₃NO₄), and 2,5-dihydroxyl-1,4-benzoquinone (C₆H₄O₄) respectively were identified during the degradation of 2-NP for the first time in the DBD with JT14 or JT17 using LC-MS. These intermediate compounds have never been reported in the literature, thereby expanding the number of BPA or 2-NP intermediates in the data base in the DBD/JT14 or DBD/nZVI system. BPA degradation proceeded via ozonation, hydroxylation, dimerization, and decarboxylation and nitration step, while 2-NP proceeded via hydroxylation, nitration and denitration respectively. Furthermore, maximum removal efficiency of BPA or 2-NP in aqueous solution using JLR alone under the optimum solution pH (3), inlet pressure (4 bar), flow rate (0.0007 m3/s) was 14.0 % and 13.2 % respectively after 80 minutes. A removal efficiency of 34.9 % was recorded for BPA while 33.2 % was achieved for 2-NP using combined JLR/UV under the same conditions as JLR alone. For the combined JLR/H₂O₂ under optimum conditions of inlet pressure (4 bar), solution pH (3) and peroxide dosage (0.34 g/L), a 51.3 % and 50.1 % removal efficiency was achieved for BPA and 2-NP respectively under same conditions relative to JLR alone. Combination of JLR/UV/H₂O₂ achieved 77.7 % (BPA) or 76.6 % (2- NP) removal efficiency under the same conditions. The combined JLR/UV/H₂O₂ process was found to be most effective combination under the optimized operating parameters due to existence of a synergetic index value of 6.42 or 6.84. This implies that JLR should be coupled with UV and H₂O₂ to achieve greater mineralization efficiency instead of using the system individually. The obtained experimental data of these combined treatment processes fitted the pseudo-first order kinetic models. The combination of the JLR/UV/H₂O₂ was found to be energy efficient and could effectively degrade BPA or 2-NP in aqueous solution to a greater extent than the JLR, JLR/UV or JLR/H₂O₂ system. However, the total organic carbon (TOC) reduction value by all combined DBD and JLR system recorded was not completely achieved due to the formation of recalcitrant intermediate compounds under the applied conditions. In conclusion, this study is reporting for the first time a combination of supported 2.4 % Ag doped TiO₂ nanocomposites with dielectric barrier discharge system for BPA/2-NP degradation in aqueous solution; a combination jet loop reactor based on impingement with in-line UV lamp and H2O2 for successfully decomposing BPA or 2-NP in aqueous solution; as well as a combination of dielectric barrier discharge system and stabilised nano zero valent iron particles, which induced a photo-Fenton process for highly effective removal of BPA or 2-NP in aqueous solution. This study conclusively supports the hypothesis that combined advanced oxidation technologies offer a sustainable and highly efficient means of achieving partial or complete removal of BPA or 2-NP in aqueous solutions. Considering all the combinations of AOTs investigated in this study, the novel DBD/photo-Fenton-induced process under optimised operating parameters was found to be the most efficient in the elimination of BPA or 2-NP in aqueous solutions. The combination of DBD with photo- Fenton like process offers a promising advanced waste water purification technology in the immediate future. Based on these findings, it is recommended that DBD should be redesigned to prevent loss of ozone and JLR system reconfigured to increase impingement and cavitational yield in order to have an effective combination treatment strategy for waste water purification especially in large scale waste water management. / National Research Foundation (NRF) and Water Research Commission, South Africa

[pt] O presente trabalho tem por objetivo analisar a degradação do fármaco Clonazepam (CZP), um dos remédios controlados mais vendidos no mundo e um possível contaminante emergente das águas residuais e de superfície. Foi realizada a degradação do composto a partir da fotólise UVC do peróxido de hidrogênio, das reações de Fenton fotoassistida (Foto-Fenton) por lâmpadas UVA, UVC, e por radiação solar, assim como pelo Sistema H2O2/Óxidos de Ferro, para efeito de comparação. Todas as análises foram conduzidas por cromatografia líquida de alta eficiência (CLAE) com detector UV. Os resultados alcançaram conversões acima de 85 por cento em boa parte dos experimentos e indicaram a cinética, em sua maioria, com ordem aparente próxima a 2 e k igual 0,95 mg. L-1. min-1 no Foto-Fenton UVC e k igual 0,02 mg.L-1.min-1 no Sistema H2O2/Óxidos de Ferro. Além disso, foi feita a análise de toxicidade utilizando sementes de alface para o H2O2/Óxidos de Fe, a fotólise UVC e para o Foto-Fenton com lâmpada UVC, com valores de inibição de crescimento de até 44 por cento. / [en] The present work aims at analyzing the degradation of the drug Clonazepam (CZP), one of the best-selling controlled drugs in the world and a possible emerging contaminant of surface and wastewater. Compound degradation was performed by UVC photolysis of hydrogen peroxide, photo-assisted Fenton reactions (Photo-Fenton) by UVA, UVC lamps, and solar radiation, as well as by the H2O2/Iron Oxides System for comparison purposes. All analyses were conducted by high performance liquid chromatography (HPLC) with UV detector. The results reached conversions above 85 percent in most of the experiments and indicated the kinetics, mostly, with apparent order close to 2 and k equal 0.95 mg. L-1. min-1 in Photo-Fenton UVC and k equal 0.02 mg.L-1.min-1 in H2O2/Iron Oxides. In addition, toxicity analysis was carried out using lettuce seeds for H2O2/Iron Oxides, UVC photolysis and UVC lamp Photo-Fenton, with growth inhibition values of up to 44 percent.

[ES] El agua se convirtió en uno de los recursos más escasos de la Tierra. Por eso es necesario desarrollar nuevas tecnologías para el tratamiento adecuado de las aguas residuales urbanas (UWW), permitiendo su reutilización. Múltiples tecnologías han demostrado ser efectivas cuando se aplican individualmente, pero a menudo no se aplican ni se integran en el tratamiento convencional de UWW, lo que resulta en la pérdida de posibles efectos sinérgicos. Por estas razones, la investigación sobre la combinación e integración de estas tecnologías es de suma importancia. Cuando se aplican de esta manera, también se conocen como Tecnologías Integradas Avanzadas. Hecho un trabajo de investigación sobre el rendimiento de una planta piloto de nanofiltración (NF) a escala piloto para UWW, seguido de la aplicación de métodos de tratamiento (químico). Los Procesos de Oxidación Avanzada (AOP), como el proceso (solar) foto-Fenton (SPF), aprovechan el ciclo catalítico del hierro (Fe2+ y Fe3+), la luz UV-vis, junto con un agente oxidante, como el peróxido de hidrógeno (H2O2), produciendo radicales hidroxilo altamente reactivos. Este proceso de foto-Fenton (solar) se aplica a un pH 3, para evitar la precipitación del hierro, o a un pH más alto mediante agentes quelantes, como el ácido etilendiamino-N, N'-disuccínico (EDDS). Los microcontaminantes (MC) usados fueron cafeína, imidacloprid, tiacloprid, carbamazepina y diclofenaco. La preconcentración es un paso esencial antes de aplicar AOP como tratamiento terciario de los efluentes de las plantas de tratamiento de aguas residuales urbanas (EDAR), ya que reduce significativamente el volumen a tratar y, por lo tanto, los costos económicos. El tratamiento de la corriente de concentrado de la NF mediante el proceso de SPF demostró ser efectivo para la eliminación de los MC mencionados anteriormente cuando se utilizó H2O2 como agente de oxidación. Por lo tanto, a una mayor degradación de los MC se adhiere una toxicidad directamente proporcionalmente menor. Las investigaciones incluyen la valorización de los efluentes EDAR mediante la recuperación de amonio, con la eliminación combinada de MC mediante NF y diferentes AOPs, con el fin de producir corrientes de permeado para la fertilización e irrigación directa de cultivos, también conocida como 'fertirrigación'. Esto incluye el proceso de SPF, pero también se combina con procesos de electrooxidación (EO). El SPF fue más efectivo al tratar las corrientes de concentrado de NF a pH circunneutro, con una concentración de MC inferior a 1 mg/L. Las corrientes de concentrado de NF altamente salinas son ideales para ser tratadas mediante procesos de EO, por sus alta conductividad, con un consumo eléctrico significativamente menor con la asistencia solar. La eficiencia de retención de MC por NF y la toxicidad después de los tratamientos con AOP también se evaluaron mediante la determinación de la fitotoxicidad del permeado. Los resultados mostraron que los permeados utilizados para los cultivos (Sorghum saccharatum, Sinapis alba, Lepidium sativum) redujeron la germinación de las semillas. Contrariamente, se observó que la irrigación con los permeados producidos generalmente promovió el desarrollo de las raíces, mientras que el desarrollo de los brotes prosperó solo cuando se usaron permeados que tenían factores de concentración inferiores al factor de concentración 2. Los estudios mostraron que los permeados deberían diluirse primero en un mínimo del 50%, para ser adecuados para la irrigación directa. El trabajo también incluyó la evaluación de una membrana de ultrafiltración (UF) cerámica foto catalítica TiO2-ZrO2 previamente desarrollada. La disminución del flujo puede revertirse cuando se irradia la membrana UF cerámica con luz en un simulador solar. La retención microbiológica de la membrana UF fue determinada utilizando una cepa bacteriana Gram negativa, Pseudomonas aeruginosa y fue capaz de retener consistentemente hasta un orden de magnitud de 1 x 104 UFC/ml. / [CA] L'aigua es va convertir en un dels productes bàsics més escassos de la Terra. Per tant, cal desenvolupar noves tecnologies, com el tractament adequat de les aigües residuals urbanes (UWW) per a la seva reutilització. Múltiples tecnologies avançades es demostren efectives quan s'apliquen únicament. Aquestes tecnologies sovint no s'apliquen ni s'integren en el tractament UWW convencional. Com a resultat, es perd possibles efectes sinèrgics. Per aquests motius, la investigació sobre la combinació i integració d'aquestes noves tecnologies és de la màxima importància. Quan s'apliquen així, aquestes tecnologies combinades també es coneixen i s'indiquen com a Tecnologies Integrades Avançades. Es va realitzar un treball de recerca sobre el rendiment d'una planta de nanofiltració (NF) a escala pilot per a la preconcentració d'UWW, seguida de l'aplicació de mètodes de tractament (químics), per tal de tractar els corrents de concentrat i permeat produïts. Els processos d'oxidació avançats (AOP), com el procés foto-Fenton (solar) (SPF), fan servir el cicle catalític del ferro (Fe2+ i Fe3+), la llum UV-vis, juntament amb un agent oxidant, com el peròxid d'hidrogen (H2O2), produint radicals hidroxil altament reactius i no selectius. Aquest procés SPF s'aplica a pH3, per tal d'evitar la precipitació del ferro, o a pH circumneutral aplicant agents quelants com l'àcid etilendiamina-N, N¿-disuccinic (EDDS). La preconcentració és un pas essencial abans d'aplicar els AOP com a tractament terciari d'efluents d'EDAR, ja que redueix significativament el volum a tractar i, per tant, els costos globals. El tractament del corrent de concentrat del NF mitjançant el procés SPF va demostrar ser eficaç per a l'eliminació de diferents microcontaminants (MC) quan s'utilitzava H2O2 com a agent d'oxidació. Per al qual una degradació de MC més alta s'adhereix a una toxicitat menor directament proporcional. Els seleccionats (MC) van ser cafeïna, imidacloprid, tiacloprid, carbamazepina i diclofenac. Els treballs de recerca posteriors van tractar la valorització dels efluents d'EDAR mitjançant la recuperació d'amoni, amb l'eliminació combinada de MC per NF i diferents AOP avançats, per tal de produir corrents permeats per a la fertilització directa dels cultius i el reg, també anomenats "fertirrigació". Inclou SPF, però també combinat amb processos d'electrooxidació (EO). El SPF va ser més eficaç quan es tractaven corrents de concentrat de NF a pH circumneutral, a una concentració de MC inferior a 1 mg/L, per obtenir una degradació ràpida de MC. Els corrents concentrats de concentrat NF altament salins són ideals per ser tractats mitjançant processos EO, alhora que posseeixen una alta conductivitat, i un menor consum elèctric significatiu per assistència solar. També es va avaluar l'eficiència de retenció de MC per NF i la toxicitat després dels tractaments amb AOP determinant la fitotoxicitat del permeat. Els resultats van mostrar que els permeats podrien reduir la germinació de llavors si s'utilitzaven per a cultius (Sorghum saccharatum, Sinapis alba, Lepidium sativum). Al contrari d'això, es va demostrar que el reg amb els permeats produïts afavoria generalment el desenvolupament de les arrels, mentre que el desenvolupament dels brots només va prosperar quan s'utilitzaven permeats que tenien factors de concentració inferiors a 2. Els estudis de toxicitat van mostrar que els corrents de permeat s'havien de diluir primer amb un mínim del 50% aigua dolça. El treball de recerca realitzat també va incloure l'avaluació d'una membrana d'ultrafiltració ceràmica (UF) fotocatalítica TiO2-ZrO2 desenvolupada prèviament. La disminució del flux es pot revertir quan la membrana fotocatalítica UF va ser irradiada per llum en un simulador solar. La retenció microbiològica de la membrana UF es va determinar mitjançant el desplegament d'una soca bacteriana gramnegativa, Pseudomonas aeruginosa, ser capaç de retenir constantment fins a un ordre de magnitud d'1 x 104 CFU/ml. / [EN] Water turned to be one of Earths scarcest commodities. Therefore, novel technologies need to be developed, as appropriate treatment of produced urban wastewaters (UWWs) for its reuse as irrigation waters or aquifer recharge. Multiple advanced technologies are proven effective when applied solely. These technologies are often not applied or integrated into conventional UWW treatment. Resulting in missing out on potential synergetic effects. For these reasons that research into the combining and integration of these novel technologies is of the utmost importance. When thus applied, these combined technologies are also known and indicated as Advanced Integrated Technologies. Research work was conducted on the performance of a pilot scale nanofiltration (NF) plant for UWW pre-concentration, followed by the application of (chemical) treatment methods, in order to treat the produced concentrate and permeate streams. Advanced Oxidation Processes (AOPs), such as the (solar) photo-Fenton process make use of the catalytic cycle of iron (Fe2+ and Fe3+), UV-vis light, along with an oxidizing agent, such as hydrogen peroxide (H2O2), producing highly reactive and non-selective hydroxyl radicals (¿OH). This (solar) photo-Fenton process is applied at acidic pH3, in order to prevent iron precipitation, or at circumneutral pH by applying chelating agents such as Ethylenediamine-N, N¿-disuccinic acid (EDDS). Preconcentration is an essential step before applying AOPs as tertiary treatment of UWWTP effluents, as it significantly lowers the to be treated volume, and therefore the overall costs. Treating the concentrate stream from the NF by the solar photo-Fenton process showed to be effective for the removal of different microcontaminants (MCs) when H2O2 was used as an oxidation agent. Opposite to that, the application of persulfate and its derived radicals showed lower degradation of the selected MC. For which a higher MC degradation is adhered to a directly proportional lower toxicity. Selected (MCs) were caffeine, imidacloprid, thiacloprid, carbamazepine, and diclofenac. Further research work covered UWWTP effluent valorization by the recovery of ammonium, with combined MC elimination by NF and different advanced AOPs, in order to produce permeate streams for direct crop fertilization and irrigation, also called 'fertigation'. Including solar photo-Fenton, but also combined with electrooxidation (EO) processes. Solar photo-Fenton was most effective when treating NF concentrate streams at circumneutral pH, at MC concentration lower than 1 mg/L, to obtain rapid MC degradation. High saline and concentrated NF concentrate streams are ideal to be treated by EO processes, while possessing high conductivity. Obtaining significant lower electric consumption by solar assistance. MC retention efficiency by NF and toxicity after AOP treatments was also assessed by determining the permeate phytotoxicity. Results showed that permeates could lower seed germination if they would be used for crops (Sorghum saccharatum, Sinapis alba and Lepidium sativum). Contrary to that, it was showed that irrigation with the produced permeates generally promoted root development, while shoot development only thrived when using permeates which had concentration factors lower than 2. Toxicity studies showed that permeate streams should first be diluted with a minimum of 50% fresh water, in order to be suitable for direct crop irrigation in agriculture. Conducted research work also included the assessment of a priorly developed (collaboration with an PhD within MSCA AQUAlity) photocatalytic TiO2-ZrO2 ceramic ultrafiltration (UF) membrane. Flux decline can be reversed when the photocatalytic UF membrane was irradiated by light in a solar simulator. Microbiological retention of the UF membrane was determined by deploying a Gram-negative bacterial strain, Pseudomonas aeruginosa (P. Aeruginosa). It was able to consistently retain till an order of magnitude of 1x10^4 CFU/ml. / This PhD Thesis has received funding from the European Union’s Horizon 2020 research and innovation program, the AQUAlity project, under the Marie SkłodowskaCurie grant agreement No 765860. Performing research work at CIEMAT – Plataforma Solar de Almería. / Deemter, RD. (2024). Application of Advanced Integrated Technologies (Membrane and Photo-Oxidation Processes) for the Removal of CECs contained in Urban Wastewater [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/203099

Cette étude porte sur l'application de différents procédés d'oxydation avancée, POA (plasma d'air humide, électro-Fenton, photo-Fenton et oxydation anodique avec BDD) pour le traitement des colorants de textile. La particularité de ces procédés tient à la génération dans le milieu d'entités très réactives et très oxydantes, les radicaux hydroxyles *OH qui sont capables d'oxyder n'importe quelle molécule organique jusqu'au stade ultime d'oxydation, c'est-à-dire la minéralisation (transformation en CO2 et H2O). Le plasma d'air humide a été appliqué pour l'oxydation d'un colorant azoïque, l'OD 61. Différents catalyseurs (Fe2+, Fe3+ et TiO2) ont été ajoutés dans leurs conditions optimisées afin d'améliorer les performances du système Glidarc. La combinaison des deux catalyseurs: Fe2+ et TiO2 a permis de décolorer 91% de l'OD 61 au bout de 3 heures et d'atteindre un taux d'abattement du COT de l'ordre de 52% après 10 heures de traitement. La méthodologie de la recherche expérimentale a été appliquée dans ce mémoire afin d'étudier l'influence de: l'intensité du courant, la concentration du colorant et le temps d'électrolyse sur la vitesse de disparition de l'OD 61 et afin de déterminer les conditions optimales de sa minéralisation. Dans les conditions optimales obtenues ([colorant] = 0,53.10-3 mol.L-1, I = 250 mA), le procédé électro-Fenton (EF) permet d'atteindre des taux de minéralisation de l'ordre de 98% dans le cas de l'OD 61 et l'AO 7 et de 88% dans le cas de l'indigo carmine. L'identification des produits intermédiaires au cours de l'électrolyse a permis de proposer un mécanisme de minéralisation de l'AO7. Les constantes cinétiques apparentes et absolues ont été déterminées. La dégradation de l'indigo a été étudiée par oxydation anodique avec BDD (OA-BDD) et par procédé photo-Fenton (PF). Cette étude a montré que l'électrolyse de l'indigo suit une cinétique de pseudo premier ordre et que le taux d'abattement du COT était de l'ordre de 97% et 63% respectivement avec OA-BDD et PF. Une étude comparative pour l'oxydation de l'AO 7 a été menée par trois procédés d'oxydation avancée: PF, OA- BDD et EF-Pt et EF-BDD. Cette étude a montré que le procédé photo-Fenton permet d'atteindre des taux d'abattement supérieurs à 90% après seulement 2 heures de traitement. Toutefois, le PF s'est révélé le plus coûteux suite à l'utilisation de la lumière artificielle UV et l'ajout des réactifs. Par ailleurs, le traitement d'un effluent réel issu de l'industrie de textile par le procédé électro-Fenton avec une anode de platine a permis la minéralisation presque totale du rejet initial (94% du COT initial ont été éliminés).

Substâncias tóxicas como o fenol e outros compostos aromáticos dificultam o tratamento de efluentes via digestores biológicos. Estes compostos tóxicos em altas concentrações são nocivos aos lodos biológicos, podendo inviabilizar por completo o tratamento. Nas últimas décadas, os Processos Oxidativos Avançados (POAs), como os processos Fenton e foto- Fenton, surgiram como alternativa para o tratamento de compostos tóxicos. Os POAs degradam os compostos orgânicos pela geração de compostos oxidantes fortes, como o radical hidroxila, a partir de reagentes como peróxido de hidrogênio. Os processos Fenton e foto-Fenton fazem uso de ferro (II), um catalisador relativamente barato, para catalisar a decomposição do peróxido de hidrogênio, reação denominada como reação de Fenton. Em virtude dos complexos mecanismos presentes nos processos Fenton e foto-Fenton, torna-se necessária uma compreensão da cinética do processo, que envolve reações térmicas e fotoquímicas, por meio de sua modelagem matemática fenomenológica. A modelagem da degradação do fenol via processos Fenton e foto-Fenton proposta por este trabalho começa pela estequiometria dos dois processos, que descreve as reações químicas, térmicas e fotoquímicas existentes. A partir destas, é possível desenvolver o modelo cinético dos processos Fenton e foto-Fenton, no qual se determina a velocidade com que estas reações ocorrem. O passo seguinte é o da modelagem hidráulica (ou de escoamento) dos reatores de processo Fenton e foto-Fenton, sendo que para o segundo processo, o modelo deve levar em conta a propagação da radiação por dentro de reator. Foram realizados 3 experimentos de degradação de fenol via processo Fenton para análise das variações das concentrações de fenol, catecol e hidroquinona. Os dados experimentais são comparados com resultados simulados com intuito do ajuste das constantes cinéticas do modelo. Com as constantes ajustadas, são realizadas comparações entre os processos Fenton e foto-Fenton para análise de suas eficiências. A partir dos modelos matemáticos dos reatores de processos Fenton e foto-Fenton, é desenvolvido um modelo de otimização baseado em superestrutura de redes de reatores para a síntese de uma planta de tratamento de efluentes contaminados com fenol. Objetivou-se a redução dos custos de capital, operação e depreciação desta planta, sujeitos às restrições de projeto e ao modelo da superestrutura, resultando em modelos de programação não-linear inteira mista. Foram geradas soluções ótimas para o tratamento de efluentes contaminados com fenol em redes de um, dois e três reatores de POAs. / Toxic substances such as phenol and other aromatic compounds make the wastewater treatment by biological (aerobic or anaerobic) digestors more difficult. These toxic compounds in high concentrations are harmful for the biological sludge and they may render the treatment impractical. In recent decades, Advanced Oxidative Processes (AOPs) appeared as an alternative for the treatment of toxic compounds. AOPs degrade the organic compounds by generating strong oxidizing compounds, such as the hydroxyl radical, from reactants such as hydrogen peroxide. The Fenton and photo-Fenton processes make use of iron (II), a relatively inexpensive catalyst, to catalyze the hydrogen peroxide decomposition, reaction known as the Fenton reaction. Because of the complex nature of the mechanisms that take place in the Fenton and photo-Fenton processes, the understanding of the process kinetics, which involves thermal and photochemical reactions, becomes necessary through its first-principle mathematical modeling. The modeling of phenol degradation by the Fenton and photo-Fenton processes proposed in this work starts with the stoichiometry of the two processes that enumerates the existing thermal and photochemical reactions. Furthermore, it is possible to develop the Fenton and photo- Fenton kinetic model, which determines the reaction rates. The next step is to model the hydraulic (or flow) behavior of the Fenton and photo-Fenton process reactor, whereas the model for the latter must consider how the radiation propagates inside the reactor. Three experiments of the phenol degradation by the Fenton process were carried out to analyze the concentration variation for phenol, catechol and hydroquinone. The experimental data are compared with simulated results aiming the estimation of the kinetic constants of the model. Using the adjusted constants, the Fenton and photo-Fenton processes were compared to analyze their efficiencies. From the mathematical models of the Fenton and photo-Fenton process reactors, an optimization model based on reactor network superstructure is developed for the synthesis of a phenol contaminated wastewater treatment plant. The objective is to minimize the plant capital, operation and depreciation costs, subject to design constraints and to the superstructure model, thus resulting in mixed integer nonlinear programming models. Optimal solutions were generated for the phenol contaminated wastewater treatment in networks with one, two and three AOP reactors.

O 2,4-diclorofenol (2,4-DCF), poluente modelo usado neste trabalho, é um composto empregado na produção de pesticidas, herbicidas e anti-sépticos, e comumente encontrado em efluentes industriais, sendo considerado um poluente prioritário devido a sua elevada toxicidade e alto poder de persistência no ambiente. Este trabalho objetivou estudar a degradação do 2,4-DCF em reator fotoquímico tubular com coletores parabólicos compostos (CPC) irradiado pelo Sol, operado em batelada com recirculação e admissão contínua de peróxido de hidrogênio à vazão de 11 mL min-1. A oxidação do poluente foi baseada no processo foto-Fenton catalisado por tris(oxalato) ferrato(III) (FeOx), investigando-se os efeitos das seguintes variáveis: concentração inicial de 2,4-DCF ([2,4-DCF] = 21-520 mgCL-1), concentrações de oxidante ([H2O2] = 9,9-130 Mm) e de fotocatalisador ([FeOx] = 0,2-1,8 mM) e área de coleta de fótons (0,196-0,98 m2), estudadas a partir de um planejamento Doehlert em múltiplos níveis. A foto-oxidação foi monitorada por medidas da concentração de carbono orgânico total (TOC) e oxigênio dissolvido (OD), tendo sido identificadas condições com remoção de TOC alcançando 99,8% em 90 minutos de tratamento. Nas análises estatísticas dos resultados, os efeitos da área de coleta de fótons e da concentração de H2O2 concordaram com o comportamento esperado, sugerindo, porém, efeitos sequestradores de radicais hidroxila quando a concentração de H2O2 é alta. A partir dos dados experimentais, obteve-se um modelo de redes neurais, usado para previsão da taxa de remoção de TOC em função do tempo. Através do método HIPR (Holdback Input Randomization Method) e dos pesos associados a cada variável de entrada da rede neural, avaliou-se a importância relativa das variáveis de entrada. De maneira geral, os resultados comprovaram a viabilidade do processo foto-Fenton catalisado por tris(oxalato) ferrato III e irradiado pelo Sol para o tratamento de efluentes aquosos contendo 2,4-diclorofenol. / 2,4-dichlorophenol (2,4-DCF), the model pollutant selected in this work, is a compound used in the production of pesticides, herbicides, antiseptics, and commonly found in industrial wastewaters. It is considered a priority pollutant due to its high toxicity and high persistence in the environment. This study investigated the degradation of 2,4-DCF in a tubular photochemical reactor with compound parabolic collectors (CPC) irradiated by the sun, operated in batch with recirculation and continuous feed of hydrogen peroxide at a flow rate of 11 mL min-1. The oxidation of the pollutant was based on the photo-Fenton process catalyzed by tris (oxalate) ferrate (III) (FeOx). The effects of the following variables were investigated: initial concentration of 2,4-DCF ([2,4-DCF] = 21-520 mgCL-1), concentrations of oxidant ([H2O2] = 9,9-130 Mm)); photocatalyst ([FeOx]= 0,2-1,8 mM)), and photon collection surface (0,196-0,98 m2), according to a Doehlert design on multiple levels. The photo-oxidation was monitored by measurements of the concentration of total organic carbon (TOC) and dissolved oxygen (OD). Conditions with TOC removal achieving 99.8% within 90 minutes of treatment were identified. The statistical analysis of the results showed that the effects of photon collection area and the concentration of H2O2 agreed with the expected behavior, but suggests scavenging effects of hydroxyl radicals when the concentration of H2O2 is high. From the experimental data, a model of neural networks was obtained and used to predict the rate of TOC removal with time. Using the method HIPR (Holdback Input Randomization Method) and the weights associated with each input variable to the neural network, the relative importance of input variables was determined. Overall, the results proved the feasibility of photo-Fenton process catalyzed by tris(oxalate) ferrate III and irradiated by the sun, for the treatment of aqueous effluents containing 2,4-dichlorophenol.

Made available in DSpace on 2014-12-17T15:41:48Z (GMT). No. of bitstreams: 1 SyllosSS_DISSERT.pdf: 3274284 bytes, checksum: efc9ef709dfd1e06b4170ed41eedf3fb (MD5) Previous issue date: 2010-02-22 / The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitablesurfactant was the EO 7 due to the lower reagent consumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min / A gera??o de res?duos na maioria dos processos industriais ? quase que inevit?vel. Na ind?stria do petr?leo, um dos grandes vil?es para o meio ambiente ? o enorme volume de ?guas produzidas nos campos de petr?leo. Este efluente apresenta composi??o complexa e aliado ao grande volume envolvido pode-se tornar bastante danoso ao meio ambiente quando descartado de forma inadequada. Esta pesquisa est? centrada na an?lise das efici?ncias dos processos de flota??o em coluna e oxida??o avan?ada por processo foto-Fenton para remo??o/degrada??o de org?nicos presentes na ?gua produzida. Uma s?rie de tensoativos derivados de ?lcool laur?lico foi utilizada na flota??o para promover a melhoria da cin?tica e efici?ncia de separa??o. Os experimentos foram realizados com efluente sint?tico contendo xileno como poluente modelo. Os dados experimentais obtidos da flota??o apresentaram cin?tica de 1? ordem, identificada pela qualidade dos ajustes lineares. As melhores condi??es encontradas foram 0,029 g.L-1 para o EO 7, 0,05 g.L-1 para o EO 8, 0,07 g.L-1 para o EO 9, 0,045 g.L-1 para o EO 10 e 0,08 g.L-1 para o EO 23 com as seguintes constantes de velocidade iguais a 0,1765, 0,1325, 0,1210, 0,1531, 0,1699 min-1, respectivamente. Para a s?rie estudada, o tensoativo mais adequado foi o EO 7 devido o menor consumo de reagente, maior constante cin?tica de separa??o e maior efici?ncia de remo??o do xileno da fase aquosa (98%). De forma similar a flota??o, o processo foto-Fenton demonstrou ser eficiente para degrada??o do xileno alcan?ando efici?ncia de mineraliza??o da carga org?nica entre 90% e 100% em 90 min