Tesis sobre el tema "Photocatalytic oxidation process"

This thesis presents the achievements pursued during the doctoral course. The work was carried out in the context of the project ERiCSol (Energia RInnovabile e Combustili SOLari), as part of the University of Trento strategic plan for the years 2017-2021. The project was conceived to establish an interdepartmental area to promote the challenge of developing scientific research and technological innovation to increase the competitiveness of Trento at national and international level in the areas of energy and environment. Among all the goals of the project, this work dedicates special attention to 1) development of novel materials for solar photocatalytic reactions and 2) use of renewable energy to push forward applications in water remediation. To accomplish these goals, the research brings a full collection of experimental activities regarding the employment of solar concentration for the environment industry and therefore this document is organized in 9 chapters. In chapter 1, it is presented the introduction outlining the overview of the environment industry, the employment of solar light as energy source and the general and specific objectives. Chapter 2 presents a literature review regarding the last 30 years of applications correlating the use of solar light towards wastewater purification. The chapter reviews the engineering features of solar collectors, photocatalyst materials employed and the panorama of the pollutants investigated up to the present date in solar photocatalysis, presenting comparisons between models and real wastewater approaches. Chapter 3 details the experimental techniques and characterizations employed to sustain the investigation proposed in the thesis. The first part of the chapter explains the features of parabolic dish solar concentrator designed and manufactured by the IdEA group at the physics department of the university of Trento. After, it is presented the pulsed laser deposition, a thin films fabrication technique employed to produce the photocatalysts used on water purification experiments. The second part of the chapter presents the description of the characterization techniques used to reveal the fabricated photocatalyst materials properties. Based on the review on the fundamentals of solar photocatalysis and the experimental techniques, chapters 4 and 5 present a discussion in the field of novel photocatalytic materials capable to operate under concentrated sunlight irradiation. Chapter 4 in special presents the investigation regarding the fabrication of tungsten trioxide (WO3) thin film coatings, bringing the novelty of using pulsed laser deposition as the fabrication method and the evaluation of this material in photocatalysis for the degradation of methylene blue dye model pollutant. Chapter 5 instead, presents the development on Zinc Oxide (ZnO) nanoparticles, bringing an innovative point of view on a “green-synthesis” approach and the material immobilization in film for heterogeneous photocatalysis routes. Chapters 6 and 7 discuss solar photocatalysis aiming to shift applications from model pollutants to real wastewater remediation conditions. Important comparisons are performed and discussed regarding the advantages and existing drawbacks. To fulfill this purpose, chapter 6 presents an application case of solar photocatalysis to the degradation of a surfactant-rich industrial wastewater whereas chapter 7 presents the approach focused on the remediation of organic lead contaminants present on a local water well site in the city of Trento. The last experimental approach of concentrated solar light is presented on chapter 8, dedicated to the application of concentrated sunlight towards waste biomass valorization. Conversely to the application on water previously described, this chapter presents the activity on designing, fabricating and coupling a hydrothermal reactor with concentrated sunlight using it as the driving force to promote degradation of grape seeds evolving into hydrochars with possible valorization of the carbonized material. Lastly, chapter 9 presents the conclusions and suggestions, this item expresses the final considerations on the results of the experimental investigations, advantages and limitations observed, and suggests possible actions for future works.

Heterogeneous photocatalysis is an advanced oxidation technology widely applied in environmental remediation processes. It is a relatively safe and affordable technology with a low impact on the environment and has found applications in a number of fields from chemical engineering, construction and microbiology to medicine. It is not catalysis in the real sense of the word as the photons which initiate the desired photocatalytic reaction are consumed in the process. The cost of these photons is by far the limiting economic factor in its application. From a technical standpoint, the inefficient use of the aforementioned photons during the photocatalytic reaction is responsible for the limited adoption of its application in industry. This inefficiency is characterised by low quantum yields or photonic efficiencies during its application. The mechanism of the technique of controlled periodic illumination which was previously proposed as a way of enhancing the low photonic efficiency of TiO2 photocatalysis has been investigated using a novel controlled experimental approach; the results showed no advantage of periodic illumination over continuous illumination at equivalent photon flux. When the technique of controlled periodic illumination is applied in a photocatalytic reaction where attraction between substrate molecules and catalyst surface is maximum and photo-oxidation by surface-trapped holes, {TiIVOH•}+ ads is predominant, photonic efficiency is significantly improved. For immobilized reactors which usually have a lower illuminated surface area per unit volume compared to suspended catalyst and mass transfer limitations, the photonic efficiency is even lower. A novel photocatalytic impeller reactor was designed to investigate photonic efficiency in gas–solid photocatalysis of aromatic volatile organic compounds. The results indicate photonic efficiency is a function of mass transfer and catalyst deactivation rate. The development of future reactors which can optimise the use of photons and maximize photonic efficiency is important for the widespread adoption of heterogeneous photocatalysis by industry.

A bench-scale tubular reactor with recirculation was built in order to study the efficiency of the photocatalytic oxidation of phenol on fluidized titanium oxide-coated silica gel beads. A UV-C lamp placed along the central vertical axes of the reactor was used as source of photons. A bed of silica gel beads was fluidized by means of fluid recirculation and forced to follow upward helical flow around the lamp. Anatase was successfully synthetized on silica gel particles of average diameters 224, 357 and 461 µm, as confirmed by scanning electron micrographs, through a sol-gel technique using a titanium (iv)isopropoxide / hydrochloric acid / ethanol precursor. Data was obtained from multiple 8-hours photocatalytic experiments using a determined mass of beads fluidized in an aqueous solution of known initial phenol concentration. Contaminant degradation with irradiation time was measured as COD. Beads that had been subjected to three consecutive coating procedures produced an 8-h removal efficiency 10% higher than beads with a single coat. 20 g L-1 of silica beads was found to be the optimum load for the experimental reactor configuration regardless of beads size, although efficiency increased with decreasing size of the latter. Experimental results confirmed that the efficiency of phenol photocatalytic degradation decreases with increasing pollutant concentration. Also, the highest removal was achieved with initial pH 3, and it decreased with increasing pH. When NaCl was added to the solution, COD removal increased with increasing salinity. Additionally, it was found that dissolved oxygen is indispensable for photocatalysis to proceed, and that saturation of the treated mixture with oxygen was effectively achieved by keeping the liquid surface in contact with pure oxygen at 1 atm. Finally, statistical analysis of the data showed that photocatalytic mineralization of phenol-derived COD under the experimental conditions follows exponential decay. Based on this finding, a correlation model was proposed for the accurate prediction (minimum R2 = 0.9840) of the COD removal efficiency of the reactor for any given initial COD.

Water pollution is an alarming problem that endangers the health of all living beings. The textile industry is listed as one of the most contaminating industries, since in order to carry out its dyeing and finishing processes, it requires a large amount of water resources; by decades, this industry has used Advanced Oxidation Processes (AOPs), since they have several advantages (e. g. destruction of toxic substances, reduction of heavy metals, allowing their use in conjunction with other processes, among others). Among the AOPs, heterogeneous photocatalysis stands out for its high efficiency for the removal of contaminants, including azo dyes. In order to perform a photocatalytic process, it is necessary to have a photoreactor, which will require a photocatalyst and at least one light source that activates the catalyst. This type of photoreactors can present several problems, such as the use of high cost photocatalysts, the generation of toxic byproducts in some low photocatalysts, the high electrical consumption caused by the use of traditional lighting sources and even difficulties with the geometry of the photoreactors. Hence the scientific community has tried to optimize the photocatalytic processes, some scientists have worked in the generation of new photocatalysts to be able to use them in wavelengths generated by low cost lighting sources (e. g. visible light), nevertheless, which in many times it increases the price of the photocatalyst. Another approach is to reduce electricity consumption by opting for the replacement of traditional lamps with low consumption lighting, for example, LED lighting; However, this substitution is currently done arbitrarily, so sometimes some authors doubt the ability to use these sources in this type of process. Moreover, when trying to improve the lighting sources, the photoreactor can be altered, so it is important to take into account its characteristics in order to achieve a significant improvement. This thesis focuses on an optoelectronic optimization to improve the efficiency of the lighting sources used in photocatalytic reactors. For this, a methodology has been generated to calculate LED arrays using uniform irradiance models, this irradiance must be homogeneous, with enough energy to photoactivate the catalyst with the aim to replace the traditional lamps, avoiding the chemical alteration of the photocatalysts; Likewise, a photocatalytic reactor has been designed and implemented on a laboratory scale with ultraviolet illumination adjusted to its characteristics (i.e. geometry, dimensions, among others) to work with a low cost photocatalyst (TiO2) in the decolorization of wastewater with textile dyes. Finally, in-situ monitoring has been designed and implemented in order to analyze the decolorization of textile water, this type of monitoring avoids the collection of water samples during the process, without altering the geometry of the reactor or reducing the volume of treated water in the reactor.
La contaminación del agua es un problema alarmante que pone en peligro la salud de todos los seres vivos. La industria textil está catalogada como una de las industrias más contaminantes, puesto que para realizar sus procesos de teñido y acabado requieren de una gran cantidad de recursos hídricos; desde hace décadas esta industria ha usado los Procesos de Oxidación Avanzada (AOPs) al presentar diversas ventajas (e. g. destrucción de sustancias tóxicas, reducción de metales pesados, permitir su uso en conjunto con otros procesos, entre otros). Entre los AOPs, sobresale la fotocatálisis heterogénea, por su alta eficiencia para la remoción de contaminantes, incluidos los colorantes azoicos. Para realizar un proceso fotocatalítico, es necesario tener un fotorreactor, el cual requerirá de un fotocatalizador y al menos una fuente de iluminación que active el catalizador. Este tipo de fotorreactores pueden presentar diversos problemas, tales como, el uso fotocatalizadores de alto costo, la generación de subproductos tóxicos en algunos fotocatalizadores de bajo, el alto consumo eléctrico causado por la utilización de fuentes tradicionales de iluminación e incluso dificultades con la geometría de los fotorreactores. Por lo tanto la comunidad científica ha intentado optimizar los procesos fotocatalíticos, algunos científicos han trabajado en la generación de nuevos fotocatalizadores para poder utilizarlos en longitudes de onda generada por fuentes de iluminación de bajo coste (e. g. luz visible), no obstante, lo que en muchas ocasiones incrementa el precio del fotocatalizador. Otro enfoque se encuentra en la reducción del consumo eléctrico optando por la sustitución de las lámparas tradicionales por iluminación de bajo consumo, por ejemplo, iluminación LED; sin embargo, actualmente esta sustitución se realiza de manera arbitraria, por lo que en ocasiones algunos autores dudan de la capacidad de utilizar estas fuentes en este tipo de procesos. Además al intentar mejorar las fuentes de iluminación puede alterarse el fotorreactor, por lo que es importante tomar en consideración sus características para lograr una mejora significativa. Esta tesis se enfoca en una optimización optoelectrónica para mejorar la eficiencia de las fuentes de iluminación utilizadas en reactores fotocatalíticos. Para ello se ha generado una metodología para calcular arreglos de LEDs utilizando modelos de irradiancia uniforme, esta irradiancia debe ser homogénea, con energía suficiente para fotoactivar el catalizador y sustituir las lámparas tradicionales, evitando la alteración química de los fotocatalizadores; asimismo, se ha diseñado e implementado un reactor fotocatalítico a escala de laboratorio con iluminación ultravioleta ajustada a sus características (geometría, dimensiones, entre otros) para trabajar con un fotocatalizador de bajo coste (TiO2) en la decoloración de agua con colorantes textiles. Para finalizar se ha diseñado e implementado un sistema de monitorización in-situ para la decoloración de aguas teñidas, este tipo de monitorización evita la toma de muestras de durante el proceso, sin alterar la geometría del reactor ni disminuir el volumen de agua tratada del reactor.

In this work, a series of simple, rapid and effective photoelectrochemical methodologies have been developed and successfully applied to the study of kinetic and thermodynamic characteristics of photocatalytic oxidation processes at TiO2 nanoparticulate films. As an application of the systematic studies of photocatalytic processes by photoelectrochemical techniques, a rapid, direct, absolute, environmental-friendly and accurate COD analysis method was successfully developed. In this work, the TiO2 nanoparticles colloid was prepared by the sol-gel method. The TiO2 nanoparticles were immobilized onto ITO conducting glass slides by dip-coating method. Thermal treatment was carried out to obtain nanoporous TiO2 films of different structures. At low calcination temperature (below 600°C), nanoporous TiO2 films of pure anatase phase were prepared. At high calcination temperature (above 600°C), nanoporous TiO2 films of mixed anatase and rutile phases were obtained. At these film electrodes, the work was carried out. By employing steady state photocurrent method and choosing phthalic acid as the model compound, the photocatalytic activity of the TiO2 nanoporous films calcined at various temperatures and for different lengths of time was evaluated. It was found that the films with mixed anatase and rutile phases calcined at high temperature exhibited high photocatalytic activity. Based on semiconductor band theory, a model was proposed, which explained well this finding. By employing linear sweep voltammetry (under illumination) and choosing glucose (an effective photohole scavenger) as a model compound, the characteristics of the photocatalytic processes at nanoparticulate semiconductor electrodes were investigated. Characteristics of the nanoporous semiconductor electrodes markedly different from bulk semiconductor electrodes were observed. That is, within a large range of electrode potentials above the flat band potential the electrodes behaved as a pure resistance instead of exhibiting variable resistance expected for bulk semiconductor electrodes. The magnitude of the resistance was dependent on the properties of the electrodes and the maximum photocatalytic oxidation rate at TiO2 surface determined by the light intensity and substrate concentration. A model was proposed, which explained well the special characteristics of particulate semiconductor electrodes (nanoporous semiconductor electrodes). This is the first clear description of the overall photocatalytic process at nanoparticulate semiconductor electrodes. The investigation set a theoretical foundation for employing photoelectrochemical techniques to study photocatalytic processes. By using the transient technique (illumination step method analogous to potential step method in conventional electrochemistry), the adsorption of a number of strong adsorbates on both low temperature and high temperature calcined TiO2 nanoporous films was investigated. Similar adsorption characteristics for different adsorbates on different films were observed. In all the cases, three different surface bound complexes were identified, which was attributed to the heterogeneity of TiO2 surface. The photocatalytic degradation kinetics of the pre-adsorbed organic compounds of different chemical nature was also studied by processing the photocurrent-time profiles. Two different photocatalytic processes, exhibiting different rate characteristics, were observed. This was, again, attributed to the heterogeneity of the TiO2 surface corresponding to heterogeneous adsorption characteristics. The catalytic first order rate constants of both fast and slow processes were obtained for different organic compounds. It was found that for different adsorbates of different chemical nature the magnitudes of rate constant for the slow kinetic process were very similar, while the magnitudes of rate constant for the fast process were significantly affected by the photohole demand characteristics of different adsorbates. Photohole demand distribution that depends on the size and structure of the adsorbed molecules was believed to be responsible for the difference. By employing steady state photocurrent method, the photocatalytic degradation kinetic characteristics of both strong adsorbates and weak adsorbates of different chemical structures were compared at pure anatase TiO2 nanoporous TiO2 films as well as at anatase/rutile mixed phase TiO2 nanoporous film electrodes. At the former electrodes for all the different organic compounds studied, the photocatalytic reaction rate increased linearly with concentration at low concentrations. Under such conditions, it was demonstrated that the overall photocatalytic process was controlled by diffusion and was independent of the chemical nature of organic compounds. However, the linear concentration range and the maximum photocatalytic reaction rate at high concentrations were significantly dependent on the chemical nature of the substrates. This was explained by the difference in the interaction of different organic compounds with TiO2 surface, the difference in their photohole demand distributions at the TiO2 surface and the difference in their nature of intermediates formed during their photocatalytic mineralization. In contrast, at the latter electrodes for the photocatalytic oxidation of different organic compounds the linear ranges (diffusion control concentration range) and the maximum reaction rates at high concentration were much larger than at the former electrodes and much less dependent on the chemical nature of the organic compounds. The spatial separation of photoelectrons and photoholes (due to the coexistence of rutile phase and anatase phase) and the increase in the lifetime of photoelectrons and photoholes are responsible for the excellent photocatalytic activity of the electrodes. By employing the thin-layer photoelectrochemical technique (analogous to the thin-layer exhaustive electrolytic technique), the photocatalytic oxidation of different organic compounds at the mixed phase TiO2 nanoporous electrodes were investigated in a thin layer photoelectrochemical cell. It was found that the charge derived from exhaustive oxidation agreed well with theoretical charge expected for the mineralisation of a specific organic compound. This finding was true for all the compounds investigated and was also true for mixtures of different organic compounds. The photocatalytic degradation kinetics of different organic compounds of different chemical identities in the thin layer cell was also investigated by the photoelectrochemical method. Two kinetic processes of different decay time constants were identified, which were attributed to the degradation of preadsorbed compounds and the degradation of compounds in solution. For the degradation of compounds in solution, a change in the overall control step from substrate diffusion to heterogeneous surface reaction was observed. For different organic compounds, the variation of the rate constant was determined by the photohole demand rather than by the chemical identities of substrates. The kinetics of the fast kinetic process, on the other hand, was greatly affected by the adsorption properties of the substrates. For the strong adsorbates, the rate was much larger than for weak adsorbates. However, the rate constant of the process was independent of the chemical identities of the substrates and the variation of the constant was also determined by the photohole demand. Based on the principles of exhaustive photoelectrocatalytic degradation of organic matter in a thin layer cell, a novel, rapid, direct, environmental-friendly and absolute COD analysis method was developed. The method was tested on synthetic samples as well as real wastewater samples from a variety of industries. For synthetic samples with given compositions the COD values measured by my method agree very well with theoretical COD value. For real samples and synthetic samples the COD values measured by my method correlated very well with those measured by standard dichromate COD analysis method.

In this work, a series of simple, rapid and effective photoelectrochemical methodologies have been developed and successfully applied to the study of kinetic and thermodynamic characteristics of photocatalytic oxidation processes at TiO2 nanoparticulate films. As an application of the systematic studies of photocatalytic processes by photoelectrochemical techniques, a rapid, direct, absolute, environmental-friendly and accurate COD analysis method was successfully developed. In this work, the TiO2 nanoparticles colloid was prepared by the sol-gel method. The TiO2 nanoparticles were immobilized onto ITO conducting glass slides by dip-coating method. Thermal treatment was carried out to obtain nanoporous TiO2 films of different structures. At low calcination temperature (below 600°C), nanoporous TiO2 films of pure anatase phase were prepared. At high calcination temperature (above 600°C), nanoporous TiO2 films of mixed anatase and rutile phases were obtained. At these film electrodes, the work was carried out. By employing steady state photocurrent method and choosing phthalic acid as the model compound, the photocatalytic activity of the TiO2 nanoporous films calcined at various temperatures and for different lengths of time was evaluated. It was found that the films with mixed anatase and rutile phases calcined at high temperature exhibited high photocatalytic activity. Based on semiconductor band theory, a model was proposed, which explained well this finding. By employing linear sweep voltammetry (under illumination) and choosing glucose (an effective photohole scavenger) as a model compound, the characteristics of the photocatalytic processes at nanoparticulate semiconductor electrodes were investigated. Characteristics of the nanoporous semiconductor electrodes markedly different from bulk semiconductor electrodes were observed. That is, within a large range of electrode potentials above the flat band potential the electrodes behaved as a pure resistance instead of exhibiting variable resistance expected for bulk semiconductor electrodes. The magnitude of the resistance was dependent on the properties of the electrodes and the maximum photocatalytic oxidation rate at TiO2 surface determined by the light intensity and substrate concentration. A model was proposed, which explained well the special characteristics of particulate semiconductor electrodes (nanoporous semiconductor electrodes). This is the first clear description of the overall photocatalytic process at nanoparticulate semiconductor electrodes. The investigation set a theoretical foundation for employing photoelectrochemical techniques to study photocatalytic processes. By using the transient technique (illumination step method analogous to potential step method in conventional electrochemistry), the adsorption of a number of strong adsorbates on both low temperature and high temperature calcined TiO2 nanoporous films was investigated. Similar adsorption characteristics for different adsorbates on different films were observed. In all the cases, three different surface bound complexes were identified, which was attributed to the heterogeneity of TiO2 surface. The photocatalytic degradation kinetics of the pre-adsorbed organic compounds of different chemical nature was also studied by processing the photocurrent-time profiles. Two different photocatalytic processes, exhibiting different rate characteristics, were observed. This was, again, attributed to the heterogeneity of the TiO2 surface corresponding to heterogeneous adsorption characteristics. The catalytic first order rate constants of both fast and slow processes were obtained for different organic compounds. It was found that for different adsorbates of different chemical nature the magnitudes of rate constant for the slow kinetic process were very similar, while the magnitudes of rate constant for the fast process were significantly affected by the photohole demand characteristics of different adsorbates. Photohole demand distribution that depends on the size and structure of the adsorbed molecules was believed to be responsible for the difference. By employing steady state photocurrent method, the photocatalytic degradation kinetic characteristics of both strong adsorbates and weak adsorbates of different chemical structures were compared at pure anatase TiO2 nanoporous TiO2 films as well as at anatase/rutile mixed phase TiO2 nanoporous film electrodes. At the former electrodes for all the different organic compounds studied, the photocatalytic reaction rate increased linearly with concentration at low concentrations. Under such conditions, it was demonstrated that the overall photocatalytic process was controlled by diffusion and was independent of the chemical nature of organic compounds. However, the linear concentration range and the maximum photocatalytic reaction rate at high concentrations were significantly dependent on the chemical nature of the substrates. This was explained by the difference in the interaction of different organic compounds with TiO2 surface, the difference in their photohole demand distributions at the TiO2 surface and the difference in their nature of intermediates formed during their photocatalytic mineralization. In contrast, at the latter electrodes for the photocatalytic oxidation of different organic compounds the linear ranges (diffusion control concentration range) and the maximum reaction rates at high concentration were much larger than at the former electrodes and much less dependent on the chemical nature of the organic compounds. The spatial separation of photoelectrons and photoholes (due to the coexistence of rutile phase and anatase phase) and the increase in the lifetime of photoelectrons and photoholes are responsible for the excellent photocatalytic activity of the electrodes. By employing the thin-layer photoelectrochemical technique (analogous to the thin-layer exhaustive electrolytic technique), the photocatalytic oxidation of different organic compounds at the mixed phase TiO2 nanoporous electrodes were investigated in a thin layer photoelectrochemical cell. It was found that the charge derived from exhaustive oxidation agreed well with theoretical charge expected for the mineralisation of a specific organic compound. This finding was true for all the compounds investigated and was also true for mixtures of different organic compounds. The photocatalytic degradation kinetics of different organic compounds of different chemical identities in the thin layer cell was also investigated by the photoelectrochemical method. Two kinetic processes of different decay time constants were identified, which were attributed to the degradation of preadsorbed compounds and the degradation of compounds in solution. For the degradation of compounds in solution, a change in the overall control step from substrate diffusion to heterogeneous surface reaction was observed. For different organic compounds, the variation of the rate constant was determined by the photohole demand rather than by the chemical identities of substrates. The kinetics of the fast kinetic process, on the other hand, was greatly affected by the adsorption properties of the substrates. For the strong adsorbates, the rate was much larger than for weak adsorbates. However, the rate constant of the process was independent of the chemical identities of the substrates and the variation of the constant was also determined by the photohole demand. Based on the principles of exhaustive photoelectrocatalytic degradation of organic matter in a thin layer cell, a novel, rapid, direct, environmental-friendly and absolute COD analysis method was developed. The method was tested on synthetic samples as well as real wastewater samples from a variety of industries. For synthetic samples with given compositions the COD values measured by my method agree very well with theoretical COD value. For real samples and synthetic samples the COD values measured by my method correlated very well with those measured by standard dichromate COD analysis method.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Environmental and Applied Science
Full Text

Philosophiae Doctor - PhD
The aim of this study was to design and build an electrohydraulic discharge reactor in such a way that the synthetic immobilized TiO2 nanophotocatalytic components could be integrated, for the production of active species such as OH radicals, ozone and hydrogen peroxide, as a cocktail to clean drinking water without the addition of chemicals. The research objectives include: • To design and construct the different AOP prototypes based on various electrode configurations and compare their operation. • To optimize the discharge parameters and conditions of the best AOP system. • To determine the effectiveness of the best prototype for the degradation of methylene blue as model pollutant. • To compare the designed AOP system with the Sodis method for the disinfection of contaminated river water. • To prepare supported TiO2 nanoparticles via electro spinning, followed by combustion and study the effect on the morphology of TiO2 nanoparticles. • To determine the stability and robustness of composite nano-crystalline TiO2 photocatalysts by sonication • To determine the enhanced effect of combining the composite TiO2 in the AOP system on degradation of methylene blue under the same conditions. • To detect the active species promoting disinfection.

Os produtos lácteos são tidos como os alimentos mais perfeitos para o homem devido ao seu alto valor nutritivo. Entretanto, esses produtos vêm refletidos na elevada carga orgânica de efluente gerado. Os Processos Oxidativos Avançados (POA) são métodos químicos baseados na geração de radicais hidroxilas, que promovem a oxidação de compostos orgânicos. O uso de semicondutores no tratamento de efluentes tem sido de grande interesse devido à sua alta eficiência, estabilidade fotoquímica, natureza não-tóxica e baixo custo, especialmente quando a luz do sol é usada como fonte de irradiação. O uso de Óxido de Zinco (ZnO), por exemplo, além de mais econômico, absorve uma fração maior de espectro UV e tem melhor desempenho em pH neutro. Este estudo consistiu em avaliar a aplicação e eficiência da fotocatálise heterogênea (POA) solar com ZnO em termos de percentual de degradação de Carga Orgânica Total (COT) para um posterior tratamento biológico aerado visando melhorar as condições de despejo do efluente de modo a preservar o ecossistema e economia dos recursos naturais. O sistema POA consistiu de um volume fixo de efluente de 3L, de uma chapa metálica 800 x 250 mm revestida com uma formulação de tinta contendo ZnO, um reservatório de vidro, uma bomba centrífuga e aberto para absorção de radiações UV solar. Os resultados foram obtidos e analisados a partir do método de planejamento de experimentos em termos de percentual de degradação de COT. O melhor resultado apresentou um percentual de degradação de COT de 31,5% onde os níves das variáveis estudadas ocorreram em pH 8,0 em chapa de ZnO com espessura de 100 micrômetros (?m), utilizando o efluente in natura e o tempo total de reação de 3 h (180min). O efluente tratado pelo POA solar com ZnO foi submetido ao tratamento biológico aerado. O pH ótimo e a concentração de lodo foram de 6,0 e 5,0 mg/L, respectivamente. O percentual de degradação de COT para os tratamentos combinados foi de 75,1 % para o efluente de laticínios utilizado neste estudo. Isto sugere que o tratamento por POA utilizando ZnO seguido de um Tratamento Biológico Aerado seria uma alternativa promissora no tratamento de efluentes de laticínios.
Dairy products are the most perfect type of food for men due to its high nutritive value reflected on its high organic load of wastewater generated. The Advanced Oxidation Processes (AOP) are chemical methods based on the generation of hydroxyls radicals that promote the oxidation of organic compounds. The use of semiconductors in wastewater treatment has been of great interest owing to its high efficiency, photochemical stability, non-toxic nature and lower costs, especially when sunlight is used as source of irradiation. The use of Zinc Oxide (ZnO), for instance, besides being more economic, it also absorbs a greater range of UV spectrum and it has a better performance on neutral pH. This study consisted in evaluating the application and efficiency of solar photocatalytic oxidation (AOP) with ZnO in percentage terms of removal of Total Organic Carbon (TOC) prior to an aerobic biological treatment aiming to improve the conditions of the disposal of this wastewater in order to conserve the water environment and saving natural resources. The AOP system consisted of a working volume of 3 L, a sheet metal 800 x 250 mm covered with a paint formula containing ZnO, a glass vessel, a pump and an open system in order to collect solar UV radiation. The results were obtained and analyzed from design of experiments in terms of percentage of removal of TOC. The maximum percentage was found to be 31.5 % of removal of TOC and at pH 8.0, thickness of the sheet containing ZnO of 100 micrometers (?m), wastewater in natura and total time of reaction of 3 h (180 min). The solar AOP with ZnO treated wastewater was subjected to an aerobic biological treatment. The optimum pH and sludge loading were of 6.0 and 5.0 mg/L, respectively. The combination of both treatments resulted in 75.1 % of removal of TOC from the dairy wastewater used in this study. This suggests that the AOP using ZnO followed by an aerobic biological treatment would be a promising alternative for the treatment of dairy wastewater.

A vinhaça é o principal resíduo obtido na produção de álcool, açúcar e aguardente, sendo considerado um efluente de alto poder poluente e fertilizante. Sem o devido tratamento, quando lançada nos rios compromete a sobrevivência de diversos seres aquáticos e quando utilizada como fertilizante, o efluente não tratado pode contaminar lençóis freáticos e afetar os seres terrestres. O objetivo deste trabalho consistiu em avaliar a eficiência e aplicação da fotocatálise heterogênea com TiO2, seguido por um tratamento biológico (lodo ativado) para a redução da carga orgânica do efluente em questão. A caracterização da vinhaça in natura e tratada foi realizada empregando-se métodos estabelecidos e otimizados [DQO, NPOC, DBO5, Análise de Elementos via Absorção Atômica, Fenol, Nitrogênio (orgânico e amoniacal) e Sólidos (ST, STF, STV)]. Por meio de planejamentos fatoriais completos foram determinadas as melhores condições experimentais posterior aos tratamentos fotocatalítico e biológico, tendo como variável resposta a redução de NPOC. Uma caracterização morfológica (DRX, BET e MEV-EDS) da estrutura de TiO2 anatase e rutilo também foi realizada. Após o processo fotocatalítico, a amostra do melhor experimento foi tratada por um processo biológico, a fim de verificar a eficiência de degradação da matéria orgânica do efluente estudado através do sistema híbrido (POA - SLA). Este sistema apresentou maior eficiência tendo como fatores do tratamento fotoquímico 180 minutos de reação, com aeração, pH 9 e efluente in natura; e pH 8 e concentração do lodo de 5 g L-1 no tratamento biológico. A redução de DBO alcançada foi superior a 80 %.
Vinasse is the main residue obtained by the production of alcohol, sugar and blue rum. It is considered a high power pollutant effluent and fertilizer. Untreated vinasse into ponds and rivers make the environment unsafe, especially, to different aquatic species and, when used as a fertilizer, the untreated effluent may contaminate freatic water beds and affect terrestrial species. The aim of this work consists of evaluating the efficiency and application of heterogeneous photocatalysis with TiO2, followed by a biological treatment (activated sludge system) to reduce organic load in the referred effluent. The characterization of vinasse in natura is carried out by the use of established and optimized methods [DQO, NPOC, DBO5, Elemental Analysis by Atomic Absorption, Phenol, Nitrogenium (organic and ammoniacal) and Solids (TS, FTS, VTS)]. Complete factorial designs indicated the best experimental conditions subsequent to photacatalytic and biological treatments providing a reduction of NPOC as a variable response. A morphological evaluation (XRD, B.E.T and SEM-EDS) of anatase and rutile phase of TiO2 structure was also performed. After the photocatalytic process, the sample of the best experiment was treated by a biological process in order to verify the degradation efficiency of the effluent organic matter studied according to the hybrid system (AOP - Activated Sludge System). This system, which presented more efficiency, had a photochemical treatment of 180 minutes carried out in aerated solutions, pH 9 and effluent in natura, while the biological treatment was performed at pH 8 and sludge concentration of 5 g L-1. The reduction of BOD was more than 80%.

This PhD thesis investigated solid and liquid waste treatment systems for Sureclean, a waste Management company based in the North of Scotland. Sureclean receives a diverse range of waste streams and the increasing need for sustainable development as well as stringent environmental legislation motivated this research to develop an integrated waste treatment system. Waste characterisation was conducted using a range of analytical instrumentation to identify the TPH, COD, heavy metals content, TOC, and particle size of Sureclean waste streams. From there, four treatment systems were investigated utilising Sureclean waste streams: mechanical separation, chemical treatment, electro-coagulation and the advanced oxidation process. Laboratory and field trials were conducted using these different treatment techniques and the analysis was performed to verify the treatment results. The result of these trials led to the development of four modular waste treatment units, that form the outcome of this research: the Sureclean Water Treatment System (SWTS), a filtration based mechanical separation system was shown to reduce the TSS, BOD and TOC content of an oily wastewater; the Sureclean Sludge Separation System (SSSTS), a chemical-enhanced filtration based system was demonstrated to reduce 52.6 % of the sewage sludge volume; the Sureclean Electro-coagulation Water Treatment System (SEWTS), a system that agglomerates colloid particles and demulsifies oil removed 99.9 % of TPH from Sureclean interceptor effluent; and the Sureclean Advanced Water Treatment System (SAWTS), an advanced oxidation process which was demonstrated to reduce the TPH of a contaminated groundwater collected from an ex-gas work. The treated effluent could be discharged to Sureclean interceptor. The four treatment units developed in this research expanded Sureclean waste treatment capabilities and an integrated system was developed to treat different waste streams and to improve the treatment efficiency thus increasing the revenue and future waste stream options for Sureclean.

Neste trabalho buscou-se estratégias que pudessem promover um aumento na aplicabilidade do processo de fotocatálise heterogênea, a fim de viabilizar seu emprego como processo alternativo para o tratamento de efluente em larga escala. Neste sentido, avaliou-se o emprego do fotocatalisador TiO2 sob a forma imobilizada e também modificado com a incorporação de materiais adsorventes. O processo de fotocatálise heterogênea, empregando tanto o fotocatalisador imobilizado em suporte de vidro quanto os sintetizados e modificados com diferentes materiais adsorventes, apresentou grande eficiência para degradação de fenol, utilizado como composto poluente modelo. As porcentagens de degradação obtidas, para soluções contendo concentração inicial igual a 250 mg L-1 de fenol, foram superiores a 80% ao final de 120 minutos de tratamento. A utilização de TiO2 sob a forma imobilizada proporcionou redução do teor de carbono orgânico dissolvido de até 59%, em 120 minutos. Quando este resultado é comparado ao obtido quando o fotocatalisador é empregado sob a forma de suspensão demonstra ser promissor, uma vez que se eliminou a etapa requerida de pós-tratamento para recuperação do fotocatalisador. Porém, a imobilização do TiO2 acarretou em um decréscimo na atividade fotocatalítica quando comparado ao material em suspensão, devido a diversos fatores, entre eles, a redução da área superficial ativa do fotocatalisador e a limitações nos processos de transferência de massa. A síntese de TiO2 incorporado a substratos porosos, foi utilizada como alternativa para tentar compensar essa redução de área superficial ativa do fotocatalisador. Nesta abordagem utilizou-se diversos materiais como substratos porosos para síntese de TiO2: óxido de alumínio, óxido de zircônio, sílica-gel, sílica mesoporosa ordenada (SMO) e carvão ativado. Dentre eles, os materiais mistos de TiO2/SMO e TiO2/carvão ativado, proporcionaram os melhores resultados frente à mineralização de fenol. A incorporação de TiO2 a materiais adsorventes, além de promover um aumento nas porcentagens de fotoxidação de fenol, demonstrou potencialidade para contornar parte das inerentes limitações causadas pelo processo de imobilização do fotocatalisador.
The main goal of this work was to find alternatives capable to promote an improvement in terms of applicability of the heterogeneous photocatalysis process, in order to make it feasible in large scale. The use of the photocatalyst TiO2 immobilized and also modificated with adsorbent materials was evaluated. The heterogeneous photocatalysis process, either using photocatalyst immobilized in glass or photocatalyst synthesized and modified with different adsorbent materials, showed good efficiency to degrade phenol, which was used as pollutant compound. The degradation percentages for solutions with initial concentration of 250 mg L-1 of phenol were above 80% after 120 minutes of treatment. The use of TiO2 under the immobilized form provided a reduction of total organic carbon levels up to 59% in 120 minutes. It is a promissory result, since it eliminated post treatment steps to recover the photocatalyst, when it is used under suspended form. However, the immobilization of TiO2 caused a decrease in photocatalyst activity compared to the suspension process. The synthesis of TiO2 with incorporation of supports to its surface was evaluated as an alternative to compensate the reduction of active surface area. In order to reach this goal, many materials were used as a porous support for synthesis of TiO2, such as: aluminum oxide, zirconium oxide, silica-gel, ordered mesoporous silica and activated carbon. Amongst them, the synthesized materials constituted of TiO2/SMO and TiO2/ activated carbon showed the best results for phenol mineralization. The incorporation of adsorbent materials to the TiO2 composition, besides to promote a raising in the phenol photoxidation, demonstrated to be a viable strategy to compensate the limitations caused by the photocatalyst immobilization process.

Este trabajo se ha centrado en la degradación de contaminantes emergentes mediante POAs, adelantándose a una posible legislación futura en este campo. En esta línea, el trabajo se enfocó en tres grandes bloques: ▪ Se estudió la degradación, a nivel de laboratorio, de un compuesto modelo, el fármaco propranolol (PRO), mediante fotocatálisis, foto-Fenton y fotólisis directa. También se llevó a cabo la fotocatálisis en planta piloto con luz solar, buscando así una aproximación a su aplicación a escala real. ▪ Se investigó la degradación de un grupo amplio de CEs (fármacos, biocidas/pesticidas e inhibidores de corrosión) encontrados en un efluente de ETAR. Los POAs utilizados fueron: UV, UV/H2O2, ultrasonidos (US) y US combinado, Fenton y foto-Fenton a pH neutro. Además, se estudió el proceso foto-Fenton en continuo, como tratamiento terciario, en una planta piloto ubicada en una ETAR. ▪ Teniendo en cuenta que una de las variables clave en los sistemas fotocatalíticos es la radiación, se aplicó y desarrolló un método actinométrico sencillo para poder hacer mediciones de la radiación en un reactor fotocatalítico cuando hay presencia de catalizador en suspensión. Tanto la fotólisis directa, como la fotocatálisis y el foto-Fenton, resultaron ser tratamientos efectivos para la eliminación de PRO (Fotocatálisis: 99%, 360 min, foto-Fenton: 99%, 15 min, fotólisis: 84%, 360 min). En el caso de la fotólisis, la mineralización obtenida fue demasiado escasa, no siendo así con los otros métodos; fotocatálisis: 58% (360 min) y foto-Fenton: 60% (60 min). En fotocatálisis, se evaluaron diferentes concentraciones de catalizador en suspensión, mineralización, biodegradabilidad y toxicidad. Se determinó el camino de degradación del PRO y se analizaron los intermedios de reacción. Se estudió la influencia de la matriz de agua; Milli-Q o agua residual. La eliminación del PRO se ajustó a una cinética de pseudo-primer orden para distintas condiciones y se calculó la cinética de Langmuir-Hinshelwood. La fotocatálisis solar resultó ser también un método efectivo en la degradación del PRO. Se observó una degradación de un 81%, tras 240 minutos, con una mineralización del 31% ([PRO]o 50 mg L-1, TiO2 0,4 g L-1). Se testaron además otras dos concentraciones de TiO2. La degradación del PRO se ajustó a una cinética de pseudo-primer orden en función de la radiación o del tiempo. Se estudió también la evolución de la biodegradabilidad. El tratamiento por foto-Fenton (pH 3) se estudió mediante un diseño factorial de 23, donde los factores a estudiar fueron las concentraciones de PRO, H2O2 y Fe2+. La máxima degradación (99%, 15 min) se obtuvo para 25 mg L-1 de PRO, 56 mg L-1 de H2O2 y 5 mg L-1 de Fe2+ (mineralización: 60%, tras 60 min). El tratamiento más eficaz para la eliminación de un grupo de CEs existentes a nivel de nanogramos por litro en un efluente de ETAR fue el foto-Fenton con luz UV a 254 nm (Reactor cilíndrico, lámpara Hg-LP-25W, volumen total irradiado 0,4 L, pH neutro). Se alcanzó una degradación media de más del 85% tras sólo 5 min de irradiación, aprovechando el hierro presente en el agua y 30 mg L-1 de H2O2. Se estudió la influencia de distintos factores: concentración inicial de H2O2, concentración de hierro, tipo de hierro empleado (Fe II-III), fuente de radiación, temperatura y oxígeno. El estudio en planta piloto para la remediación de CEs en efluente de ETAR, se encontró que, empleando UV (254 nm) + H2O2 + Fe (existente en el agua) a pH natural, se alcanzaban degradaciones superiores al 80% con tiempos de residencia muy bajos. El tratamiento más económico correspondía a la adición de 50 mg L-1 de H2O2 y un tiempo de residencia de 10 s. En el bloque del estudio de la medida de la radiación en sistemas fotocatalíticos, se demostró que la actinometría del o-NB puede ser empleada en presencia del TiO2 en suspensión para hacer medidas de radiación en el fotorreactor, ya que el o-NB no se destruye por fotocatálisis.
This work focuses on the remediation of emergent contaminants by using AOPs. In this way, the study has been divided in three parts: ▪ Degradation of a model compound, the pharmaceutical propranolol (PRO), at laboratory scale, by photocatalysis, photo-Fenton and direct photolysis. Photocatalysis was also studied in a solar pilot plant, to approximate to real application. ▪ Remediation of a large ECs group including pharmaceuticals, biocides/pesticides and corrosion inhibitors, found in a MWTP effluent. AOPs employed were UV, UV/H2O2, ultrasound (US) and combined US, Fenton and photo-Fenton at neutral pH. ▪ Radiation is a key parameter in photocatalytic systems. Thus, an actinometric method was studied to determine the radiation entering a photreactor with the presence of a catalyst (TiO2) in suspension. The work on PRO remediation showed that direct photolysis, photocatalysis and photo-Fenton could degrade PRO (photocatalysis: 99%, 360 min, photo-Fenton: 99%, 15 min, photolysis: 84%, 360 min). Employing direct photolysis, mineralization obtained was poor (6%, 360 min). Good mineralizations were achieved with photocatalysis (58%, 360 min) and photo-Fenton (60%, 60 min). Solar photocatalysis was also found to be an efficient method for PRO remediation. After 240 min, 81% of degradation was reached, with a mineralization of 31%. In the remediation of a ECs group found in a MWTP effluent (at nanograms per litre), the most efficient treatment was the photo-Fenton with UV at 254 nm. The average degradation after 5 min was 85% (30 mg L-1 of H2O2 + iron present in the wastewater). Influence of different parameters was studied: H2O2 initial concentration, iron concentration and type (Fe II-III), radiation source, temperature and oxygen. The study of a ECs group remediation at pilot showed that the treatment with UV (254 nm) + H2O2 + Fe (not added but present in WW) at natural pH, leaded to degradations higher tan 80% with very low residence times. The most economical treatment needed 50 mg L-1 of H2O2 and a residence time of 10 s. In the section of the radiation measurement in photocatalytic systems, it was demonstrated that the o-NB actinometry could be used to measure the involved radiation when there is TiO2 in suspension present inside the photoreactor.

Os processos oxidativos avançados (POAs) têm sido apontados como alternativa eficiente para a degradação de poluentes recalcitrantes. Entre os POAs, a fotocatálise utilizando luz solar vem sendo muito estudada tendo em vista sua aplicação no tratamento de efluentes aquosos contendo pesticidas. No presente trabalho, estudou-se a degradação do herbicida amicarbazona (AMZ) por meio do processo TiO2/UV em um reator com coletores parabólicos compostos irradiados por luz solar. Os experimentos foram realizados segundo uma matriz Doehlert para o estudo da influência da concentração inicial de AMZ (20-100 mg L-1), da concentração de catalisador (0,1-1 g L-1) e do número de tubos expostos à luz solar (1-9). Amostras retiradas ao longo do tempo foram analisadas quanto às concentrações de AMZ e de carbono orgânico total (TOC). As medidas radiométricas realizadas indicaram que a radiação UVB-UVA correspondeu em média a ca. 4% da radiação solar total incidente entre 310-2800 nm; a actinometria de ferrioxalato indicou fluxo fotônico médio de 3,58×10-5 mol fótons m-2 s-1 para dias ensolarados típicos. O processo TiO2/UV mostrou-se eficiente para degradação do pesticida, que foi totalmente removido antes de 45 minutos de tratamento, para as seguintes condições: [AMZ]0=21,3 mg L-1; [TiO2]=0,5 g L-1; e 7 tubos. Contudo, nesse caso houve apenas ca. 24% de mineralização e na grande maioria dos casos os valores de TOC permaneceram praticamente constantes, o que indica a formação de sub-produtos recalcitrantes, cuja toxicidade e biodegradabilidade devem ser caracterizadas. A análise estatística dos resultados confirma os efeitos importantes da concentração inicial do pesticida e do número de tubos expostos (volume irradiado), cujo aumento permite compensar a menor incidência de radiação solar. Em alguns experimentos os resultados sugeriram que a degradação da AMZ foi favorecida pela maior concentração de TiO2. Na grande maioria dos casos os valores de ACM foram inferiores a 50 m2 kg-1, o que torna este parâmetro interessante para aumento de escala de processos fotocatalíticos irradiados por luz solar empregados no tratamento de efluentes aquosos contendo amicarbazona.
Advanced oxidative processes (AOP) have been considered as an efficient alternative for the degradation of recalcitrant pollutants. Photocatalysis using solar radiation has been studied for the treatment of wastewaters containing pesticides. In this work, the degradation of the herbicide amicarbazone (AMZ) by the TiO2/UV process was studied in a reactor equipped with compound parabolic collectors irradiated by solar light. The experiments were carried out according to a Doehlert matrix to study the effects AMZ initial concentration (20-100 mg L-1), catalyst concentration (0.1-1 g L-1), and number of tubes exposed to solar light (1-9). Samples were analyzed for AMZ and total organic carbon (TOC) concentrations. Radiometric measurements indicated that UVB-UVA radiation corresponded in average to about 4% of the solar radiation between 310-2800 nm; ferrioxalate actinometry resulted in an average photonic flux of 3.58×10-5 mol fótons m-2 s-1 for typical sunny days. The TiO2/UV process showed to be efficient for the degradation of the pesticide, which was completely removed before 45 minutes of treatment, for the following conditions: [AMZ]0=21.3 mg L-1; [TiO2]=0.5 g L-1; and 7 tubes. However, in this case only ca. 24% of mineralization was achieved, and in most cases TOC values remained practically constant, indicating the formation of recalcitrant by-products whose toxicity and biodegradility should be characterized. Statistical analysis of the results confirmed important effects of pesticide initial concentration and number of tubes exposed (irradiated volume), whose increase enables to compensate the lower incidence of solar radiation. Some experimental results suggested that AMZ degradation was favored by higher TiO2 concentrations. In most cases the values of ACM were lower than 50 m2 kg-1, in such a way that this parameter is interesting for scale-up of solar irradiated photocalytic processes used in the treatment of amicarbazone-containing wastewaters.

Orientador: Rodnei Bertazzoli
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica
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Resumo: Em aterros, quando o lixo depositado entra em decomposição, se forma o chorume, um líquido escuro e de odor desagradável, potencial patogênico e toxicológico que pode conter compostos orgânicos, metais pesados e outros íons e que se não adequadamente tratado pode causar problemas de caráter sanitário e ambiental. Métodos de oxidação química ou biológica habitualmente utilizados apresentam dificuldade para tratar chorume de aterros antigos. Visando a obtenção de um método de tratamento complementar ou alternativo, neste trabalho utilizou-se um sistema fotoeletroquímico em escala piloto de 18 L operando em modo contínuo com reciclo, composto por reator tubular com eletrodos comerciais ADE de Ti/70TiO2-30RuO2 e lâmpada ultravioleta para degradar chorume bruto de um aterro sanitário municipal. Esta configuração possui o diferencial de utilizar um sistema compacto, com eletrodo não-solúvel de longo tempo de vida útil e eliminar a necessidade de separação do semicondutor da solução após o tratamento. Foram comparados os processos fotocatalítico, eletrolítico e eletrolítico assistido por fotocatálise heterogênea com e sem a adição de fotocatalisador TiO2, determinando-se a eficiência do sistema por meio de análises de cor, DBO, DQO, toxicidade aguda, Carbono Orgânico Total, pH, temperatura, amônia e cloreto. O sistema foi otimizado em termos de densidade de corrente de eletrólise, tempo de tratamento e vazão da solução. Foram testados os valores 300, 1000,2000 e 3000 L h-1 nas densidades de corrente de 13,25, 39, 48, 78, 90 e 116 mA cm-2. No tratamento eletrolítico, em 180 min de processamento a 116,0 mA cm-2 e 2000 L h-1 foi possível remover de 86 a 1 00% da cor, 33 a 73% do COT, 31 a 90% da DQO e 31 a 100% da amônia do chorume. O comportamento cinético para remoção da cor, COT e DQO foi de segunda ordem, com constantes aparentes de velocidade de remoção variando entre 1,58.10-4 e 3,79.10-5 ma-1m s-1 2,13.10-8 e 2,92.10-9 m4s-1g-1 e 1,40.10-8 e 2,07.10-9 m4s-1g-l respectivamente. As remoções de amônia e cloreto seguiram comportamento cinético de primeira ordem, sendo que a constante média de velocidade de remoção de amônia variou entre 6,87.10-5 e 3,46.10-6 m s-1. Também, foram observadas reduções da DBO, da toxicidade e remoção de metais. Esta forma de tratamento não apresenta problemas posteriores em relação à geração de lodo ou subprodutos tóxicos, sendo indicada como complementar ao tratamento biológico
Abstract: Sanitary landfills are the major method used today for the disposal and management of municipal solid waste. Decomposition of waste and rainfall generate leachate at the bottom of landfills, causing groundwater contamination. The leachate is a dark grey, foul smelling solution and it can be considered a complex effluent, often containing organic compounds, heavy metals, and many other soluble compounds. Furthermore, leachate presents high values of biological oxygen demand (BOD), chemical oxygen demand (COD) and, because of its toxic potential, it may represent an environmental problem. Biological and chemica1 oxidation commonly used in the treatment have not entirely efficient in degrading old landfill leachate. Moreover, the process is sensitive to variable organic 10008 and different flow rates. In this study, leachate from an old age municipal landfill site was treated by photo-electrochemical oxidation in a pilot scale flow reactor (18 L), using DSA anode and UV radiation. The adopted system is small, compact, long service-life electrodes and separation between of cata1yst from solution is not necessary. By using photocatalytic, electrolytic and photo-assisted electrolytic processes, the effect of current density and flow rate on COD, BOD, total organic carbon, color, ammonia and toxicity removal was investigated. At a current density of 116.0 mA cm-l, flow rate of 2000 L h-1 and 180 min of processing, removal of 86-100% of color, 33-73% of TOC, 31-90% of COD and 31-100% of ammonia were achieved. Removal rates for color, TOC and COD presented a second-order kinetic, with apparent kinetic constants among 1,58.10-4 - 3,79.10-5 ma-lm s-l, 2,13.10-8 - 2,92.10-9 m4s-1g-1 and 1,40.10-8 - 2,07.10-9 m4s-1g-1 respectively. The ammonia and chloride removal followed a first-order kinetic, with apparent kinetic constants ranging from 6,87.10-5 to 3,46.10-6 m s-1. Furthermore, BOD, toxicity and metallic ions were also removed. This process of treatment doesn't show further problems related to sludge production or toxic by-products, been appointed as complementary to traditional biological systems. Besides the high energy consumption, the process proved effectiveness in degrading leachate, despite this effluent' s usual refractoriness to treatment
Doutorado
Materiais e Processos de Fabricação
Doutor em Engenharia Mecânica

Cette étude s’inscrit dans la thématique du développement de méthodes économiquement viables de traitement de la pollution des eaux usées réfractaires aux procédés (biologiques) classiques. Les technologies d’oxydation avancée intégrant une phase hétérogène telles que l’ozonation catalytique ou la photocatalyse font partie des techniques les plus efficaces. L’ozonation a été couplée avec un matériau issu du recyclage et de la valorisation de déchets de Côte d’Ivoire. L’objectif de cette étude était d’élaborer des méthodes hybrides couplant l’adsorption et ces méthodes d’oxydation avancée pour éliminer des micropolluants organiques phénolés. La molécule de 2,4-diméthylphénol (2,4-DMP) a été choisie comme polluant modèle et les essais ont été réalisés sur une solution aqueuse synthétique de 2,4-DMP et sur une eau usée réelle contenant ce micropolluant. La première partie du travail a consisté en l’élaboration du matériau innovant, dans des conditions opératoires variables. Les charbons actifs ont été préparés à partir de branches de rônier et de tiges de bambou. La caractérisation texturale, structurale et physicochimique des adsorbants a été réalisée avec les techniques classiques, montrant d’excellentes propriétés, notamment des surfaces BET supérieures à 840 m2.g-1. Les matériaux élaborés ont été testés dans un procédé d’adsorption du 2,4-DMP, montrant de bonnes capacités d’élimination, autant avec la solution aqueuse synthétique qu’avec l’effluent réel. Ces essais ont permis de sélectionner un charbon actif à base de branches de rônier (CAR) pour les tests de procédés d’oxydation. L’efficacité de l’apport de ce charbon actif a été testée sur un pilote de traitement, couplant l’ozonation et l’adsorption. Deux modes de couplage ont été testés, un traitement simultané ozonation/adsorption et un traitement séquentiel ozonation suivie de l’adsorption et les comparaisons avec un procédé d’ozonation simple ont été analysées. Dans les deux cas, l’ajout de charbon actif a eu un effet positif sur la cinétique globale de dégradation de la molécule de 2,4- diméthylphénol avec cependant un résiduel de COT difficile à éliminer. Il a été démontré que ce charbon actif était promoteur de radicaux libres, agissant aussi bien en phase homogène qu’hétérogène. Quatre mécanismes ont ainsi pu être mis en évidence dans le phénomène d’élimination du micropolluant : l’adsorption, l’oxydation moléculaire et l’oxydation radicalaire homogène et hétérogène. Enfin, des essais de dégradation photocatalytique ont été menés avec un catalyseur composite, TiO2/charbon actif (fibres) et avec du TiO2 en poudre et déposé sur plaque de verre. L’irradiation a été effectuée avec une lampe UV dans un réacteur batch classique, donnant de bonnes efficacités puis avec un panneau de LEDs à 365 nm dans un réacteur plan fonctionnant en boucle fermée. Deux modes de fonctionnement ont été testés : un mode simultané adsorption/photocatalyse qui n’a pas permis de mettre en évidence l’apport de l’irradiation et un mode séquentiel. Ce second mode opératoire a permis de mettre en évidence l’effet photocatalytique du dépôt pour une durée d’irradiation suffisamment longue
This study is part of the development of new economically viable methods of treating water pollution that is refractory to conventional (biological) processes. Advanced oxidation technologies integrating a heterogeneous phase such as catalytic ozonation or photocatalysis are among the most effective techniques. The ozonation was coupled with a material resulting from the recycling and the valorization of waste of Côte d’Ivoire. The objective of this study was to develop hybrid methods coupling adsorption and these advanced oxidation methods to remove phenol organic micropollutants. The 2,4-dimethylphenol molecule (2,4-DMP) was chosen as a model pollutant and the tests were carried out on a synthetic aqueous solution of 2,4-DMP and on a real wastewater containing this micropollutant. The first part of the work involved the development of the innovative material, under varying operating conditions. Activated carbons were prepared from branches of rônier and bamboo stems. The textural, structural and physicochemical characterization of the adsorbents has been carried out using conventional techniques, showing excellent properties, especially BET surfaces greater than 840 m2.g-1. The materials developed were tested in a 2,4-DMP adsorption process, showing good removal abilities, both with the synthetic aqueous solution and with the actual effluent. These tests made it possible to select an activated carbon based on rônier branches (ACR) for the oxidation process tests. The effectiveness of the input of this activated carbon was tested on a treatment pilot, coupling ozonation and adsorption. Two coupling modes were tested, simultaneous ozonation/adsorption treatment and sequential ozonation treatment followed by adsorption and comparisons with a simple ozonation process were analyzed. In both cases, the addition of activated carbon had a positive effect on the overall degradation kinetics of the 2,4-dimethylphenol molecule, with, however, a TOC residual difficult to remove. This activated carbon has been shown to be a promoter of free radicals, active in both homogeneous and heterogeneous phases. Four mechanisms have thus been demonstrated in the micropollutant elimination phenomenon: adsorption, molecular oxidation and homogeneous and heterogeneous radical oxidation. Finally, photocatalytic degradation tests were conducted with a composite catalyst, TiO2/activated carbon (fibers) and with TiO2 powder and deposited on a glass plate. The irradiation was carried out with a UV lamp in a conventional batch reactor, giving good efficiencies then with a LEDs panel at 365 nm in a closed-loop reactor. Two modes of operation were tested: a simultaneous adsorption/photocatalysis mode which did not make it possible to highlight the contribution of the irradiation and a sequential mode. This second procedure made it possible to demonstrate the photocatalytic effect of the deposit for a sufficiently long duration of irradiation

Ce travail de thèse est consacré à l'élaboration de membrane photocatalytique à partir de nanoparticules de TiO2 obtenues par voie sol-gel (système TTIP-eau). Les sols sont préparés dans un réacteur à micro-mélange rapide (turbulent). L'effet de l'hydrodynamique au sein de différents mélangeurs (T simple, T chicanes, T rétrécissement) sur la morphologie et l'activité photocatalytique de nanoparticules déposées sur des plaques d'α-alumine a été étudié. Les dépôts de TiO2 ont été réalisés durant la période d'induction de la réaction sol-gel. Le mélange des réactifs a été simulé en utilisant un logiciel de modélisation numérique (modèle k-ε), Les différences hydrodynamiques au sein du micro-mélange a seulement un impact significatif sur le temps de stabilité des nanoparticules (période d'induction). Des couches minces et des membranes photo-actives ont été réalisées en vue du couplage membrane et réaction photocatalytique. Ces membranes ont été caractérisées et testées en photocatalyse. Elles ont montrées de bonnes photo-activités. Des tests de couplage direct séparation/photodégradation ont été réalisés sur des solutions aqueuses d'acide orange 7. Ce dispositif expérimental a permis de mettre en évidence une augmentation de flux de perméation significative avec de l'eau et en présence de colorant en solution. L'effet de la concentration et du pH de la solution a été évalué sur les flux de perméat et sur la photodégradation
This PhD work is devoted to the elaboration of photocatalytic membranes using TiO2 nanoparticles synthetized by sol-gel process (titanium tetra-isopropoxyde precursor – water). Sols are prepared in sol-gel reactor with rapid turbulent micro-mixing. The effect of hydrodynamic using 3 T mixers (T simple, T with 3 baffles and T with narrow) during the mixing was studied with k-ε modeling Computational fluid Dynamics (CFD), as well as the morphology and the photo-activity of thin layers deposited on alumina support during induction period. Differences on hydrodynamic during micro-mixing have only impact on the time of nanoparticles stability (induction period). Photo-active thin layers and membranes are synthesized for coupling membrane separation and photocatalytic reaction. Photocatalytic activities of thin layers and membranes are performed with an aqueous solution of acid orange 7. Significant increases of permeate flux are observed during the filtration of water and solution containing dye. Effects of concentration and pH are evaluated on permeation flux and photodegradation

Im Rahmen der vorliegenden Arbeit wurden zwei verschiedene Klassen oxidischer Nanomaterialien nasschemisch synthetisiert und strukturell-morphologisch charakterisiert. Zum einen betrifft dies TiO2-, TiO2/SiO2-, Ag/TiO2- und Pd/TiO2-Sole, welche die photokatalytisch aktive Modifikation Anatas in nanokristalliner Form enthalten und über einen solvothermalen Sol-Gel-Prozess hergestellt werden konnten. Im Hinblick auf eine potentielle Anwendung in der Desinfektionstechnologie und für den Abbau organischer Umweltschadstoffe wurde die photokatalytische Aktivität von Pulvern und Beschichtungen auf Textil durch E. coli-Abtötung bzw. Modellfarbstoffabbau untersucht. Im Weiteren wurde die antimikrobielle Aktivität pyroelektrischer LiNbO3- und LiTaO3-Pulvermaterialien unter zyklischer thermischer Anregung nachgewiesen. Diese als Pyroelektrokatalyse bezeichnete Nutzung des pyroelektrischen Effektes in einem katalytischen bzw. elektrochemischen Prozess ist dabei von grundlegender Neuheit. Aufsetzend auf den physiko-chemischen Grundlagen dieses Phänomens wurde eine Hypothese des Mechanismus entwickelt und in Analogie zur Photokatalyse diskutiert
This thesis deals with two classes of oxidic nanomaterials that were synthesized by chemical solution routes and characterized with respect to structure and morphology. Sols of TiO2, TiO2/SiO2, Ag/TiO2 and Pd/TiO2 containing the photocatalytically active modification anatase in nanocrystalline form were prepared via a solvothermal sol-gel process. With regard to potential application in disinfection and environmental remediation technology the photocatalytic activity of powders and coatings on textile was investigated by means of E. coli decomposition and organic dye degradation. Further the antimicrobial activity of pyroelectric LiNbO3 and LiTaO3 powder materials under cyclical thermal excitation was demonstrated. In this context the application of the pyroelectric effect in a catalytic or electrochemical process – termed as pyroelectrocatalysis – is of fundamental novelty. Based on the physico-chemical principles of the phenomenon a hypothesis of the mechanism was developed and discussed in analogy with photocatalysis

This research work discusses the removal of organic pollutants specifically diclofenac and acid blue-25 using chalcogenide semiconductors. Semiconductors are materials that absorb light of specific energy and potentially degrade these organic pollutants into smaller compounds that are not toxic such as carbon dioxide and water.
Civil and Chemical Engineering

碩士
弘光科技大學
環境工程研究所
103
Abstact Wastewater from textile dyeing industry contents various chemicals such as dyestuffs and dyeing add agent which is hard to be proper treated and sometime toxic or carcinogenic. The target pollutant in this work is Acid Blue 113 (AB113) azodye. In this study, two different oxidants, i.e. sodium persulfate and Oxone, were used under UV irradiation to produce sulfate radicals to decolorize and mineralize AB113 dye wastewater. In control experiments, Oxone itself with 6.3mM concentration can decolorize AB113 effectively. Integrating persulfate or Oxone with UV irradiation can decolorize AB113 to colorless (under 550 ADMI unit). However, for TOC removal, only UV/persulfate system can mineralize AB113 up to 95%, but Oxone shows less removal efficiency. Under high UV dosage of 40W, both persulfate and Oxone can decolorize AB113 in 10 min. On the other hand, UV/persulfate can mineralize TOC for 100 mg/L AB113, but UV/Oxone system can only mineralize TOC up to 50 mg/L AB113. It shows that Oxone has limited mineralization capability. Adjust pH from 2-10, makes TOC removal enhancement for persulfate system. In contrast, adjust pH reduces TOC removal efficiency down to less than 40% for UV/Oxone system.

Algal infestation in water bodies causes the release of soluble organic compounds that impact negatively on the taste and odour of the water. With increasing pollution in water bodies and increasing nutrient loading from agricultural activities, most water reservoirs in South Africa and around the world have become affected by this problem. In this study, an advanced oxidation process (AOP), namely, photocatalysis was evaluated for its potential to degrade aromatic compounds; and taste and odour causing bi-cyclic compounds originating from algae. Semiconductor photocatalysis is an environmentally friendly technology requiring no chemical inputs which is capable of completely mineralising organic pollutants to CO2 and H2O thereby eliminating production of unwanted by-products. Although processes involved in the photo-degradation have been reported for a wide range of pollutants, the degradative pathway in this process has not been fully established. In this study, compounds including phenol, 2-chlorophenol, 4-chlorophenol and nitrophenol were successfully eliminated from simulated wastewater. Degradation of geosmin at an environmentally significant initial concentration of 220 ng/L to levels below the lowest detectable concentration was achieved with an optimum catalyst concentration of 60 mg/L at a rate of 14.78 ng/L/min. Higher catalysts loading above 60 mg/L resulted in a decrease in degradation rates. An increase in initial geosmin concentration resulted in a decrease in rates. Ionic species commonly found in surface waters (HCO3 -, and SO4 2-) significantly reduced the efficiency of geosmin degradation. Degradation of geosmin produced acyclic intermediates from ring fission tentatively identified as 3,5-dimethylhex-1-ene, 2,4-dimethylpentan-3-one, 2-methylethylpropanoate and 2-heptanal. The results obtained indicate that the degradation of organic pollutants in aqueous solution is as a result of synergic action from hydroxyl radicals, positive holes and direct photolysis by UV radiation, though the predominant pathway of degradation is via hydroxyl radicals in solution. Major aromatic intermediates of phenol degradation include catechol, resorcinol and hydroquinone produced in the order catechol > resorcinol > hydroquinone. All three are produced within 2 minutes of photocatalytic reaction of phenol and remain in solution until all phenol is degraded in aerated systems. Production of resorcinol in non-aerated systems is transient, further supporting the hydroxyl radical dominant reaction pathway.
Thesis (PhD)--University of Pretoria, 2014.
gm2014
Chemical Engineering
unrestricted

Im Rahmen der vorliegenden Arbeit wurden zwei verschiedene Klassen oxidischer Nanomaterialien nasschemisch synthetisiert und strukturell-morphologisch charakterisiert. Zum einen betrifft dies TiO2-, TiO2/SiO2-, Ag/TiO2- und Pd/TiO2-Sole, welche die photokatalytisch aktive Modifikation Anatas in nanokristalliner Form enthalten und über einen solvothermalen Sol-Gel-Prozess hergestellt werden konnten. Im Hinblick auf eine potentielle Anwendung in der Desinfektionstechnologie und für den Abbau organischer Umweltschadstoffe wurde die photokatalytische Aktivität von Pulvern und Beschichtungen auf Textil durch E. coli-Abtötung bzw. Modellfarbstoffabbau untersucht. Im Weiteren wurde die antimikrobielle Aktivität pyroelektrischer LiNbO3- und LiTaO3-Pulvermaterialien unter zyklischer thermischer Anregung nachgewiesen. Diese als Pyroelektrokatalyse bezeichnete Nutzung des pyroelektrischen Effektes in einem katalytischen bzw. elektrochemischen Prozess ist dabei von grundlegender Neuheit. Aufsetzend auf den physiko-chemischen Grundlagen dieses Phänomens wurde eine Hypothese des Mechanismus entwickelt und in Analogie zur Photokatalyse diskutiert.
This thesis deals with two classes of oxidic nanomaterials that were synthesized by chemical solution routes and characterized with respect to structure and morphology. Sols of TiO2, TiO2/SiO2, Ag/TiO2 and Pd/TiO2 containing the photocatalytically active modification anatase in nanocrystalline form were prepared via a solvothermal sol-gel process. With regard to potential application in disinfection and environmental remediation technology the photocatalytic activity of powders and coatings on textile was investigated by means of E. coli decomposition and organic dye degradation. Further the antimicrobial activity of pyroelectric LiNbO3 and LiTaO3 powder materials under cyclical thermal excitation was demonstrated. In this context the application of the pyroelectric effect in a catalytic or electrochemical process – termed as pyroelectrocatalysis – is of fundamental novelty. Based on the physico-chemical principles of the phenomenon a hypothesis of the mechanism was developed and discussed in analogy with photocatalysis.