Thesis (MScFoodSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Large volumes of high strength wastewater are generated annually by distilleries. Treatment of this wastewater is essential to increase its reuse potential. Anaerobic digestion (AD) has been widely applied as high strength wastewater treatment. Additionally, grain distillery wastewater (GDWW) is high in fats, oils and grease (FOG) which can cause problems during AD. Pre-treatment is therefore often required to make the AD process more efficient. The overall objective of this study was to investigate the operational efficiency of upflow anaerobic sludge blanket (UASB) reactors while treating GDWW as substrate. The first aim was to investigate the pre-treatment of the GDWW specifically for the removal of FOG by evaluating the effect of pH adaption, coagulant concentration and ozone (O3) dosages on the FOG reduction efficiency. Secondly, the effect of two different pre-treatments (only coagulant and coagulant and ozone) on the subsequent UASB treatment step was investigated. The pH of raw GDWW (pH 3.4) was adapted to three different pH values (5.0, 6.0, and 7.0) and the coagulant, aluminium chlorohydrate (ACH) (140 mg.L-1), was added. To make the process more economically viable, the lowering the coagulant concentration (to 100 mgACH.L-1) was also investigated. Optimal reductions for chemical oxygen demand (COD) (33.2% ± 4.93), total suspended solids (TSS) (91.9% ± 1.73) and FOG (84.1% ± 1.98) were, however, achieved at a higher coagulant concentration of 140 mgACH.L-1, and at a wastewater pH of 7.0. The effect of additional ozone treatment was also investigated. Maximum reductions for the ozone treatment were obtained at 100 mgO3.L-1 for COD (3.6% ± 4.08), and at 900 mgO3.L-1 for TSS (27.7% ± 5.58) and FOG (23.9% ± 1.83). The ozone treatment was most efficient for FOG reduction (in terms of mg FOG reduced per mg ozone) at 100 mgO3.L-1. An ozone dosage of 300 mgO3.L-1, was decided on based on economic feasibility, findings in literature on toxicity of ozone and the potential degradation of recalcitrant compounds at this dosage. The final pre-treatment thus included pH adaption to 7.0, coagulant dosage of 140 mgACH.L-1, and an ozone dosage of 300 mgO3.L-1. The second part of this study involved the operation of two 2 L laboratory scale UASB reactors for 277 days. The substrate of the first reactor contained GDWW that had only undergone coagulant pre-treatment (Rcontrol), while the substrate of the second UASB reactor consisted of GDWW that had undergone coagulant and ozone pre-treatment (Rozone). Both reactors treated the pre-treated GDWW successfully at ca. 9 kgCOD.m-3d-1. COD reductions of 96% for Rcontrol and 93% for Rozone, were achieved. FOG reductions (%) showed variations throughout the study and maximum reductions of 88% and 92% were achieved for Rcontrol and Rozone, respectively. The Rozone produced more biogas, but the methane content was similar for both reactors. The additional ozone pre-treatment did not show any added benefits to the reactor performance results. UASB granule washout in Rcontrol did, however, suggest possible toxicity of unsaturated fatty acids present in the non-ozonated substrate. The feasibility of FOG removal was shown as both reactors successfully treated pre-treated GDWW. Ozonation, after a coagulant dosage, which resulted in further reduction in the FOG content of the GDWW, is thus not essential to ensure the success of an anaerobic digestion step. Ozonation of the pre-treated GDWW could, however, be beneficial to gas production and the efficiency of a tertiary biological process. / AFRIKAANSE OPSOMMING: Groot volumes hoë-sterkte afloopwater word jaarliks deur distilleerderye opgelewer. Die behandeling van hierdie afloopwater is noodsaaklik om die hergebruiksmoontlikheid daarvan te verhoog. Die toepassing van anaërobiese vertering (AV) is wydverspreid in hoë-sterkte afloopwaterbehandeling. Graandistillerings-afloopwater (GDAW) is boonop hoog in vette, olies en ghries (VOG), wat probleme kan veroorsaak tydens AV. Voorbehandeling word dus dikwels verlang om die AV meer doeltreffend te maak. Die oorhoofse doelstelling van hierdie studie was om die doeltreffendheid van opvloei-anaërobieseslykkombers- (OAS-) reaktore wat GDAW as substraat behandel, te ondersoek. Die eerste mikpunt was om die voorbehandeling van die GDAW, te ondersoek vir die verwydering van VOG. Dit is uitgevoer deur die uitwerking van pH aanpassing, koagulantkonsentrasie en osoon(O3)dosis op VOG vermindering te evalueer. Tweedens is die uitwerking van twee verskillende voorbehandelings (slegs koagulant asook koagulant en osoonbehandeling) op die opvolgende OAS-behandelingsstap ondersoek. Die pH van rou GDAW (pH 3.4) is aangepas tot drie verskillende pH waardes (5.0, 6.0 en 7.0) en die koagulant, aluminium-chlorohidraat (ACH), is bygevoeg (140 mg.L-1). Om die proses meer ekonomies uitvoerbaar te maak is ‘n verlaagde koagulantkonsentrasie (verlaag tot 100 mgACH.L-1) ook ondersoek. Die optimale afnames vir chemiese suurstofvereiste (CSV) (33.2% ± 4.93), totale oplosbare vastestowwe (TOV) (91.9% ± 1.73) en VOG (84.1% ± 1.98) is egter bereik teen ‘n hoër koagulant konsentrasie van 140 mgACH.L-1, en teen ‘n afloopwater-pH van 7.0. Die uitwerking van ‘n bykomende osoonbehandeling is ook ondersoek. Die hoogste afnames tydens die osoonbehandeling is bereik teen 100 mgO3.L-1 vir CSV (3.6% ± 4.08), en teen 900 mgO3.L-1 vir TOV (27.7% ± 5.58) en VOG (23.9% ± 1.83). Die osoonbehandeling was mees doeltreffend vir VOG (in terme van mg VOG verwyder per mg osoon) teen 100 mgO3.L-1. Daar is besluit op ‘n van 300 mgO3.L-1, as gevolg van die ekonomiese uitvoerbaarheid, bevindinge in literatuur vir die toksisiteit van osoon, en die moontlike afbraak van moeilik-afbreekbare komponente teen hierdie dosis. Die finale voorbehandeling het dus bestaan uit ‘n aanpassing van die afloopwater-pH na 7.0, ‘n koagulantdosis van 140 mgACH.L-1, en ‘n osoondosis van 300 mgO3.L-1. Tydens die tweede gedeelte van hierdie studie is twee 2 L laboratoriumskaal OAS reaktore bedryf vir 277 dae. Die substraat van die eerste reaktor het GDAW bevat wat slegs ‘n koagulant-voorbehandeling ondergaan het (Rkontrole), terwyl die substraat van die tweede OAS-reaktor GDAW bevat het wat koagulant- en osoon-voorbehandeling ondergaan het (Rosoon). Beide reaktore het die voorbehandelde-GDAW suksesvol behandel teen ‘n organieseladingstempo van ca. 9 kgCSV.m-3d-1. Afnames in CSV van 96% vir Rkontrole en 93% vir Rosoon, is bereik. Tydens die studie is deurlopende wisseling in VOG verwydering (%) waargeneem, en die hoogste verwyderings wat bereik is, is onderskeidelik 88% en 92% vir Rkontrole en Rosoon. Die Rosoon het meer biogas geproduseer, maar die metaanpersentasie was soortgelyk vir beide reaktore. Die osoon-voorbehandeling het nie enige toegevoegde voordele getoon in die reaktorprestasie resultate nie. Die uitwas van die OAS-granules vir die Rkontrole het egter moontlike toksisiteit van onversadigdevetsure aangedui, wat moontlik teenwoordig kon wees in die nie-geösoneerde substraat. Die uitvoerbaarheid van VOG verwydering is getoon aangesien beide reaktore voorbehandelde GDAW suksesvol behandel het. Osonering, wat verdere afname in die VOG inhoud van GDAW teweeggebring het (na ‘n koagulant dosis), is dus nie noodsaaklik vir die suksesvolle verloop van ‘n anaërobiese-verteringsstap nie. Osonering van die voorbehandelde GDAW kan egter voordelig wees vir gasvorming, en kan ook verder die doeltreffendheid van ‘n tersiêre biologiese behandeling verhoog.

A indústria farmacêutica acarreta a geração de uma quantidade significante de resíduos potencialmente poluidores. Ao serem lançados em corpos d\'água, os efluentes das indústrias farmacêuticas provocam desequilíbrio no ambiente, por transportarem compostos de difícil degradação. A ocorrência desses resíduos no ambiente pode favorecer a resistência de microrganismos frente a esses fármacos, além de causar problemas de ordem toxicológica a determinados organismos vivos. No intuito de minimizar os impactos causados pelos despejos dos efluentes desta atividade industrial, torna-se necessário estudar tratamentos alternativos para degradação de tais resíduos. Esta pesquisa teve como proposta avaliar um Processo Oxidativo Avançado: Ozonição Catalítica Homogênea em presença de íons Fe2+ como técnica para tratamento de efluente veterinário, para tanto foram estudados três diferentes reatores em sistema contínuo. Na primeira etapa do estudo, foi definido o modelo de reator mais adequado para o tratamento desse efluente farmacêutico veterinário. Na segunda etapa do estudo, utilizou-se um planejamento fatorial fracionado 24-1 para otimizar as variáveis do processo: pH, concentração de Fe2+ g/L, potência do ozonizador (vazão mássica de O3) e vazão de saída do efluente do reator. A eficiência do tratamento foi avaliada por meio da redução de Carbono Orgânico Total (COT) (%). Este estudo mostrou que a condição experimental na qual se observou a maior porcentagem de redução de COT (46,14%) ocorreu quando se combinou pH 4,0, [Fe2+] de 0,5 g/L, vazão de saída do reator de 1,23 L/h e potência do ozonizador de 56W. A avaliação estatística desse planejamento apontou para uma nova configuração experimental na qual se obteve 55,24% de redução de COT, degradação do ativo Fenbendazol de 71,24% e degradação do ativo Triclabendazol de 95,68%. Essa nova configuração combinou pH 4,0, [Fe2+] de 0,1g/L, vazão de saída do reator de 1,85 L/h e potência de 56W. / The pharmaceutical industry generates a significant amount of potentially polluting waste. When released into stream, the pharmaceutical effluents cause imbalance in the environment, transporting compounds are difficult to degrade. The occurrence of these residues in the environment can improve the microbial resistance of these drugs and cause toxicological implication of certain organisms. In order to minimize the impacts caused by discharges of effluents of this industrial activity, it is necessary to study alternative treatments for degradation of the waste. The purpose of this work was to evaluate proposed system using continuous reactors as one treatment technique Advanced Oxidative Process: Catalytic Homogeneous Ozonization with Fe2+. In the first stage of the study, the reactor model more suitable for treatment of this veterinary pharmaceutical effluent. In the second stage of the study, used a design factorial 24-1to optimize the variables of the process: pH, concentration of Fe2+ g/L, ozoniser power and output flow reactor. The efficiency of the treatment was evaluated by the reduction of Total Organic Carbon rate (TOC) (%). This study showed that the experimental condition in which it was observed the highest percentage of TOC reduction (46.14%) occurred when combined pH 4.0, [Fe 2 +] 0.5 g / L, the output flow reactor 1.23 L / h and ozoniser power of 56W. The statistical evaluation of this planning pointed to a new experimental setup in which we obtained 55.24% reduction of TOC, degradation of drug Fenbendazole 71.24% and degradation of 95.68% drug Triclabendazole. This new configuration combined pH 4.0, [Fe 2 +] of 0.1 g / L, output flow reactor of 1.85 L / h and ozoniser power of 56W.

Com o objetivo do entendimento do modo pelo qual são formadas as diferentes morfologias dos óxidos de lantanídeos obtidos a partir da calcinação de citratos, neste trabalho foram sintetizados óxidos de lantanídeos (La2O3, CeO2, Pr6O11, Nd2O3, Sm2O3 e Eu2O3) a partir da calcinação dos respectivos citratos. Durante a síntese da série dos sais [LnCit.xH2O], uma nova série de sais com a composição [Ln2(HCit)3.2H2O] foi isolada e caracterizada para (Ln = La, Ce, Pr, Nd, Sm, Eu). Em contraste com os sais amorfos [LnCit.xH2O] configurando agregados irregulares, os sais [Ln2(HCit)3.2H2O] são cristalinos com hábitos cristalinos fibrosos. Os estudos térmicos destes sais mostraram perfis distintos de decomposição térmica em atmosfera de ar. A decomposição da espécie amorfa fornece itaconatos de lantanídeos, seguido pela formação do oxicarbonato de lantanídeo e finalmente o respectivo óxido. A espécie cristalina, por sua vez, se decompõe, formando oxalato de lantanídeos seguido pela formação de oxicarbonato e posteriormente óxido. A morfologia dos óxidos de lantanídeos foi investigada utilizando microscopia eletrônica de varredura. Esta técnica mostrou a correlação entre as morfologias dos óxidos e as dos respectivos precursores obtidos a partir da calcinação dos diferentes citratos. Enquanto a calcinação dos sais amorfos formado por partículas irregularmente formadas resultou em óxidos com partículas irregulares, a calcinação dos citratos cristalinos, com partículas fibrosas, resultou na formação de óxidos com partículas fibrosas. Isso sugere fortemente que a morfologia dos precursores age como molde na formação dos óxidos dando origem a partículas com morfologias hierarquicamente similares. Foram conduzidos testes catalíticos de ozonização de fenol em meio ácido utilizando, as diferentes morfologias do CeO2. Todos os tipos morfológicos do CeO2 mostraram excelente atividade, proporcionando taxas de mineralização de aproximadamente 100%, contra 60% da ozonização na ausência de catalisador. O óxido tipo 2, proveniente do precursor [Ce2(HCit)3.2H2O] mostrou a mais alta ela foi de 5,1 unidade de (Kcorr / min-1.m-2.10-3) atividade. As diferentes atividades aprtesentadas pelas diferentes morfologias dos óxidos foram atribuídas às quantidades de Ce(III) como centro ativo na superfície os óxidos. Estas diferentes quantidades de Ce (III), estimadas por luminescência óptica e o Uv/Vis, foram atribuídas aos diferentes teores de carbono nos precursores que competem pelo oxigênio durante a calcinação. Isso leva à estabilização de Ce(III) e vacâncias de oxigênio na superfície dos óxidos. / With the aim of understanding the way that the morphologies of lanthanide oxides are influenced by precursors two series of lanthanide citrates were synthesized, characterized and used as precursors in the synthesis of these oxides through calcinations (La2O3, CeO2, Pr6O11, Nd2O3, Sm2O3 and Eu2O3) . A new series of lanthanide citrates with formula [Ln2(HCit)3.2H2O] was synthesized and characterized. Compared to amorphous [LnCit.xH2O], these new salts have a fibrous morphology pointed out by SEM analysis. Thermal analysis show that [LnCit.xH2O] decompose through two major steps: itaconates, oxycarbonates and finally lanthanide oxides. [Ln2(HCit)3.2H2O], on the other hand, decompose through two distinct steps: oxalates, oxycarbonates and lanthanide oxides. The morphology of lanthanide oxides was investigated using scanning electron microscopy. A correlation between the morphologies of the oxides and their precursors could be found. While amorphous citrates consisting of irregular shaped particles give rise to irregular shaped oxides particles, calcinations of fibrous crystalline salts series led to fibrous crystalline oxide shaped particles. These results strongly suggest that the morphology of a citrate polymeric precursor acts as a template, producing to hierarchically similar particles. Acid catalytic ozonation of phenol using three morphologies of CeO2 were carried out. All tested oxides show high activity providing 100% of mineralization of phenol, whereas without catalyst only 60% of mineralization was observed. The oxide synthesized from [Ce2(HCit)3.2H2O] shows the higher activity per surface area. CeO2 synthesized from [CeCit.xH2O] shows intermediary activity per surface area. The internal combustion synthesized CeO2 showed the worst activity. The different activities showed by the three morphological forms of CeO2 were attributed to the presence of different Ce(III) amounts in the surface of catalysts. The quantities of Ce(III) were estimated by luminescence and the results agreed very well with the activity of catalysts. The different Ce(III) contents in the precursors were attributed to different carbon contents in the precursor, which compet for oxygen of environment during calcinations, leading to stabilization of Ce(III) and vacancies in the oxides.

Neste trabalho focou-se na preparação de materiais com aplicação em processos de tratamento de compostos orgânicos poluentes. Especificamente, buscou-se correlacionar as propriedades físicas e químicas dos materiais com as suas respostas catalíticas nos processos de fotocatálise heterogênea e de ozonização. Empregando-se o método de precipitação, preparou-se óxidos mistos de TiO2 e CeO2 em diferentes proporções. A caracterização destes materiais mostrou uma correlação entre a formação de partículas anisotrópicas, com morfologia do tipo bastão, e a capacidade de degradação de fenol pelo processo de fotocatálise heterogênea. Em particular, obteve-se 70% de degradação de fenol para o material com 20% CeO2. A interação entre o TiO2 e CeO2 também foi estudada em materiais preparados pelo método sol-gel. A presença do CeO2 retardou a transformação do polimorfo anatásio para rutilo, bem como manteve a estrutura de poros quando os matareriais foram calcinados a 650 ºC. Esta maior estabilidade possui relação com as propriedades fotocatalíticas dos materiais calcinados. Degradou-se 77% de fenol com o fotocatalisador 0,5% CeO2. Fotocatalisadores híbridos de SiMgOx e TiO2 foram preparados pela deposição de diferentes quantidades de TiO2 em placas de sepiolitas por slip-casting. Avaliou-se os materiais híbridos na degradação de ar contaminado com tricloroetileno (TCE) pelo processo de fotocatálise heterogênea. Observou-se uma dependência entre a espessura da camada de TiO2 e a taxa de degradação e mineralização do TCE, obtendo-se até 100% de degradação do TCE. Os materiais híbridos também tiveram suas propriedades catalíticas avaliadas na fotodegradação de TCE utilizando radiação solar. A combinação das propriedades de adsorção da sepiolita e fotocatalíticas do TiO2 possibilitaram 100% de degradação do TCE via incidência de radiação solar. O estudo de materiais híbridos também foi realizado com a preparação de esferas híbridas de carbono e CeO2. Este novo material foi preparado em uma única etapa, pelo método hidrotermal, sem a necessidade de emprego de solventes orgânicos. As esferas híbridas foram aplicadas na degradação de solução aquosa de ácido salicílico pelo processo de ozonização. As esferas eram, possívelmente, formadas por um core de carbono com nanopartículas de CeO2 dispersas em sua superfície hidrofílica. O efeito sinérgico entre a estrutura de carbono e o CeO2 resultou em um aumento de 25% na mineralização da solução de ácido salicílico pelo processo de ozonização. / This study was focused on the preparation of materials applied to the treatment of organic pollutant compounds. The main idea was to correlate the physical and chemical properties of these materials with their catalytic responses in heterogeneous photocatalysis and ozonation processes. Using the precipitation method, TiO2 and CeO2 mixed oxides were prepared in different proportions. The characterization of these materials showed a correlation between the formation of anisotropic rod-like particles and the capacity of degradation of phenol by a heterogeneous photocatalysis process. It was actived 70% of phenol degradation using the material with 20% CeO2. The interaction between TiO2 and CeO2 was also studied in materials prepared by the sol-gel method. The presence of CeO2 retarded the transition from anatase to rutile polymorphic, as well as maintained the porous structure when the materials were calcinated at 650 ºC. This major stability is related to the photocatalytic properties of the calcinated materials. For instance, 77% of the phenol was degraded using the 0.5% CeO2 photocatalyst. Hybrid photocatalysts composed by SiMgOx and TiO2 were prepared by depositing different amounts of TiO2 on sepiolite plates by slip-casting method. The performances of hybrid materials were evaluated by the degradation of contaminated air with trichloroethylene (TCE) using the heterogeneous photocatalysis process. A correlation between the thickness of the TiO2 layer and the degradation and mineralization rates of TCE was observed, obtaining up to 100% degradation of the TCE. Also, the catalytic properties of the hybrid materials were evaluated by TCE photodegration using solar radiation. A combination of the adsorption properites of the sepiolite and the photocatalytic properties of TiO2 allowed up to 100% of TCE degradation under incidence of solar radiation. The study of hybrid materials was also carried out with the preparation of carbon and CeO2 hybrid spheres. This novel material was prepared in one-pot step, using the hydrothermal method, without organic solvents. The hybrid spheres were used in the degradation of aqueous solution of salicylic acid by the ozonization process. The spheres were possibly formed by a core containing carbon with CeO2 nanoparticles dispersed on their hydrophilic surface.The synergetic effect between the carbon structure and the CeO2 resulted in an increase of 25% in the salicylic acid solution mineralization.

No presente trabalho foi estudada a utilização do ozônio como auxiliar no pós-tratamento de reatores anaeróbios por reatores de lodos ativados. Foi estudada a influência da ozonização no aumento da biodegradabilidade da matéria orgânica recalcitrante de efluente anaeróbio antes de ser submetido ao tratamento aeróbio. A pesquisa foi dividida em três etapas. Na primeira e segunda etapas foram utilizados quatro amostras, uma bruta e três ozonizadas com dosagens de 5, 10 e 15 mg O3/L. As amostras da primeira e segunda etapa tiveram tempos de ozonização de 30 e 50 minutos, respectivamente. Os reatores de lodos ativados tiveram tempo de retenção celular de 10 dias e tempo de detenção hidráulica de 24 horas. Na terceira etapa foram utilizadas três amostras, uma bruta e duas ozonizadas cuja dosagem de ozônio foi de 15 mg/L, valor que obteve melhores resultados nas etapas anteriores. Os tempos de ozonização de cada amostra foram de 30 e 50 minutos. Nesta fase, o reator de lodos ativados teve tempo de retenção celular de 10 dias e tempo de detenção hidráulica de 12 horas. Entretanto, amostras ozonizadas submetidas a pós-tratamento em reator de lodos ativados, apresentaram aumento da biodegradabilidade quando expostas a maiores tempos de ozonização. A alimentação do reator de lodos ativados com amostras ozonizadas trouxe benefícios ao seu desempenho. / On this research was studied the utilization of ozone as auxiliary on the post-treatment of anaerobics reactors by activated sludges reactors. It was studied the influence of ozonization of anaerobic effluent before being submitted to an aerobic treatment on the increase of the biodegradability of recalcitrant organic matter. The research was divided in three stages. In the first and second stage was used four samples, one brute and three ozonizades with doses of 5, 10 and 15 mg O3/L. The samples used on first and second stages had being ozonization times of 30 and 50 minutes, respectively. The activated sludges reactors had time of cellular retention of 10 days and hydraulic time of detention of 24 hours. On the third stage were used three samples, one brute and two ozonizades whose doses of ozone was of 15 mg/L, this value achieved the best results in the previous stages. The ozonizations times of each sample were of 30 and 50 minutes. On this stage the activated sludges reactors had time of cellular retention of 10 days and hydraulic time of detention of 12 hours. It was observed that ozonizades samples submitted to post-treatment in activated sludges reactors presented increase of the biodegradability when exposed at largest times of ozonization. The feeding of activated sludges reactors with ozonizades samples benefit its perfomance.

Neste trabalho focou-se na preparação de materiais com aplicação em processos de tratamento de compostos orgânicos poluentes. Especificamente, buscou-se correlacionar as propriedades físicas e químicas dos materiais com as suas respostas catalíticas nos processos de fotocatálise heterogênea e de ozonização. Empregando-se o método de precipitação, preparou-se óxidos mistos de TiO2 e CeO2 em diferentes proporções. A caracterização destes materiais mostrou uma correlação entre a formação de partículas anisotrópicas, com morfologia do tipo bastão, e a capacidade de degradação de fenol pelo processo de fotocatálise heterogênea. Em particular, obteve-se 70% de degradação de fenol para o material com 20% CeO2. A interação entre o TiO2 e CeO2 também foi estudada em materiais preparados pelo método sol-gel. A presença do CeO2 retardou a transformação do polimorfo anatásio para rutilo, bem como manteve a estrutura de poros quando os matareriais foram calcinados a 650 ºC. Esta maior estabilidade possui relação com as propriedades fotocatalíticas dos materiais calcinados. Degradou-se 77% de fenol com o fotocatalisador 0,5% CeO2. Fotocatalisadores híbridos de SiMgOx e TiO2 foram preparados pela deposição de diferentes quantidades de TiO2 em placas de sepiolitas por slip-casting. Avaliou-se os materiais híbridos na degradação de ar contaminado com tricloroetileno (TCE) pelo processo de fotocatálise heterogênea. Observou-se uma dependência entre a espessura da camada de TiO2 e a taxa de degradação e mineralização do TCE, obtendo-se até 100% de degradação do TCE. Os materiais híbridos também tiveram suas propriedades catalíticas avaliadas na fotodegradação de TCE utilizando radiação solar. A combinação das propriedades de adsorção da sepiolita e fotocatalíticas do TiO2 possibilitaram 100% de degradação do TCE via incidência de radiação solar. O estudo de materiais híbridos também foi realizado com a preparação de esferas híbridas de carbono e CeO2. Este novo material foi preparado em uma única etapa, pelo método hidrotermal, sem a necessidade de emprego de solventes orgânicos. As esferas híbridas foram aplicadas na degradação de solução aquosa de ácido salicílico pelo processo de ozonização. As esferas eram, possívelmente, formadas por um core de carbono com nanopartículas de CeO2 dispersas em sua superfície hidrofílica. O efeito sinérgico entre a estrutura de carbono e o CeO2 resultou em um aumento de 25% na mineralização da solução de ácido salicílico pelo processo de ozonização. / This study was focused on the preparation of materials applied to the treatment of organic pollutant compounds. The main idea was to correlate the physical and chemical properties of these materials with their catalytic responses in heterogeneous photocatalysis and ozonation processes. Using the precipitation method, TiO2 and CeO2 mixed oxides were prepared in different proportions. The characterization of these materials showed a correlation between the formation of anisotropic rod-like particles and the capacity of degradation of phenol by a heterogeneous photocatalysis process. It was actived 70% of phenol degradation using the material with 20% CeO2. The interaction between TiO2 and CeO2 was also studied in materials prepared by the sol-gel method. The presence of CeO2 retarded the transition from anatase to rutile polymorphic, as well as maintained the porous structure when the materials were calcinated at 650 ºC. This major stability is related to the photocatalytic properties of the calcinated materials. For instance, 77% of the phenol was degraded using the 0.5% CeO2 photocatalyst. Hybrid photocatalysts composed by SiMgOx and TiO2 were prepared by depositing different amounts of TiO2 on sepiolite plates by slip-casting method. The performances of hybrid materials were evaluated by the degradation of contaminated air with trichloroethylene (TCE) using the heterogeneous photocatalysis process. A correlation between the thickness of the TiO2 layer and the degradation and mineralization rates of TCE was observed, obtaining up to 100% degradation of the TCE. Also, the catalytic properties of the hybrid materials were evaluated by TCE photodegration using solar radiation. A combination of the adsorption properites of the sepiolite and the photocatalytic properties of TiO2 allowed up to 100% of TCE degradation under incidence of solar radiation. The study of hybrid materials was also carried out with the preparation of carbon and CeO2 hybrid spheres. This novel material was prepared in one-pot step, using the hydrothermal method, without organic solvents. The hybrid spheres were used in the degradation of aqueous solution of salicylic acid by the ozonization process. The spheres were possibly formed by a core containing carbon with CeO2 nanoparticles dispersed on their hydrophilic surface.The synergetic effect between the carbon structure and the CeO2 resulted in an increase of 25% in the salicylic acid solution mineralization.

Com o objetivo do entendimento do modo pelo qual são formadas as diferentes morfologias dos óxidos de lantanídeos obtidos a partir da calcinação de citratos, neste trabalho foram sintetizados óxidos de lantanídeos (La2O3, CeO2, Pr6O11, Nd2O3, Sm2O3 e Eu2O3) a partir da calcinação dos respectivos citratos. Durante a síntese da série dos sais [LnCit.xH2O], uma nova série de sais com a composição [Ln2(HCit)3.2H2O] foi isolada e caracterizada para (Ln = La, Ce, Pr, Nd, Sm, Eu). Em contraste com os sais amorfos [LnCit.xH2O] configurando agregados irregulares, os sais [Ln2(HCit)3.2H2O] são cristalinos com hábitos cristalinos fibrosos. Os estudos térmicos destes sais mostraram perfis distintos de decomposição térmica em atmosfera de ar. A decomposição da espécie amorfa fornece itaconatos de lantanídeos, seguido pela formação do oxicarbonato de lantanídeo e finalmente o respectivo óxido. A espécie cristalina, por sua vez, se decompõe, formando oxalato de lantanídeos seguido pela formação de oxicarbonato e posteriormente óxido. A morfologia dos óxidos de lantanídeos foi investigada utilizando microscopia eletrônica de varredura. Esta técnica mostrou a correlação entre as morfologias dos óxidos e as dos respectivos precursores obtidos a partir da calcinação dos diferentes citratos. Enquanto a calcinação dos sais amorfos formado por partículas irregularmente formadas resultou em óxidos com partículas irregulares, a calcinação dos citratos cristalinos, com partículas fibrosas, resultou na formação de óxidos com partículas fibrosas. Isso sugere fortemente que a morfologia dos precursores age como molde na formação dos óxidos dando origem a partículas com morfologias hierarquicamente similares. Foram conduzidos testes catalíticos de ozonização de fenol em meio ácido utilizando, as diferentes morfologias do CeO2. Todos os tipos morfológicos do CeO2 mostraram excelente atividade, proporcionando taxas de mineralização de aproximadamente 100%, contra 60% da ozonização na ausência de catalisador. O óxido tipo 2, proveniente do precursor [Ce2(HCit)3.2H2O] mostrou a mais alta ela foi de 5,1 unidade de (Kcorr / min-1.m-2.10-3) atividade. As diferentes atividades aprtesentadas pelas diferentes morfologias dos óxidos foram atribuídas às quantidades de Ce(III) como centro ativo na superfície os óxidos. Estas diferentes quantidades de Ce (III), estimadas por luminescência óptica e o Uv/Vis, foram atribuídas aos diferentes teores de carbono nos precursores que competem pelo oxigênio durante a calcinação. Isso leva à estabilização de Ce(III) e vacâncias de oxigênio na superfície dos óxidos. / With the aim of understanding the way that the morphologies of lanthanide oxides are influenced by precursors two series of lanthanide citrates were synthesized, characterized and used as precursors in the synthesis of these oxides through calcinations (La2O3, CeO2, Pr6O11, Nd2O3, Sm2O3 and Eu2O3) . A new series of lanthanide citrates with formula [Ln2(HCit)3.2H2O] was synthesized and characterized. Compared to amorphous [LnCit.xH2O], these new salts have a fibrous morphology pointed out by SEM analysis. Thermal analysis show that [LnCit.xH2O] decompose through two major steps: itaconates, oxycarbonates and finally lanthanide oxides. [Ln2(HCit)3.2H2O], on the other hand, decompose through two distinct steps: oxalates, oxycarbonates and lanthanide oxides. The morphology of lanthanide oxides was investigated using scanning electron microscopy. A correlation between the morphologies of the oxides and their precursors could be found. While amorphous citrates consisting of irregular shaped particles give rise to irregular shaped oxides particles, calcinations of fibrous crystalline salts series led to fibrous crystalline oxide shaped particles. These results strongly suggest that the morphology of a citrate polymeric precursor acts as a template, producing to hierarchically similar particles. Acid catalytic ozonation of phenol using three morphologies of CeO2 were carried out. All tested oxides show high activity providing 100% of mineralization of phenol, whereas without catalyst only 60% of mineralization was observed. The oxide synthesized from [Ce2(HCit)3.2H2O] shows the higher activity per surface area. CeO2 synthesized from [CeCit.xH2O] shows intermediary activity per surface area. The internal combustion synthesized CeO2 showed the worst activity. The different activities showed by the three morphological forms of CeO2 were attributed to the presence of different Ce(III) amounts in the surface of catalysts. The quantities of Ce(III) were estimated by luminescence and the results agreed very well with the activity of catalysts. The different Ce(III) contents in the precursors were attributed to different carbon contents in the precursor, which compet for oxygen of environment during calcinations, leading to stabilization of Ce(III) and vacancies in the oxides.

A indústria farmacêutica acarreta a geração de uma quantidade significante de resíduos potencialmente poluidores. Ao serem lançados em corpos d\'água, os efluentes das indústrias farmacêuticas provocam desequilíbrio no ambiente, por transportarem compostos de difícil degradação. A ocorrência desses resíduos no ambiente pode favorecer a resistência de microrganismos frente a esses fármacos, além de causar problemas de ordem toxicológica a determinados organismos vivos. No intuito de minimizar os impactos causados pelos despejos dos efluentes desta atividade industrial, torna-se necessário estudar tratamentos alternativos para degradação de tais resíduos. Esta pesquisa teve como proposta avaliar um Processo Oxidativo Avançado: Ozonição Catalítica Homogênea em presença de íons Fe2+ como técnica para tratamento de efluente veterinário, para tanto foram estudados três diferentes reatores em sistema contínuo. Na primeira etapa do estudo, foi definido o modelo de reator mais adequado para o tratamento desse efluente farmacêutico veterinário. Na segunda etapa do estudo, utilizou-se um planejamento fatorial fracionado 24-1 para otimizar as variáveis do processo: pH, concentração de Fe2+ g/L, potência do ozonizador (vazão mássica de O3) e vazão de saída do efluente do reator. A eficiência do tratamento foi avaliada por meio da redução de Carbono Orgânico Total (COT) (%). Este estudo mostrou que a condição experimental na qual se observou a maior porcentagem de redução de COT (46,14%) ocorreu quando se combinou pH 4,0, [Fe2+] de 0,5 g/L, vazão de saída do reator de 1,23 L/h e potência do ozonizador de 56W. A avaliação estatística desse planejamento apontou para uma nova configuração experimental na qual se obteve 55,24% de redução de COT, degradação do ativo Fenbendazol de 71,24% e degradação do ativo Triclabendazol de 95,68%. Essa nova configuração combinou pH 4,0, [Fe2+] de 0,1g/L, vazão de saída do reator de 1,85 L/h e potência de 56W. / The pharmaceutical industry generates a significant amount of potentially polluting waste. When released into stream, the pharmaceutical effluents cause imbalance in the environment, transporting compounds are difficult to degrade. The occurrence of these residues in the environment can improve the microbial resistance of these drugs and cause toxicological implication of certain organisms. In order to minimize the impacts caused by discharges of effluents of this industrial activity, it is necessary to study alternative treatments for degradation of the waste. The purpose of this work was to evaluate proposed system using continuous reactors as one treatment technique Advanced Oxidative Process: Catalytic Homogeneous Ozonization with Fe2+. In the first stage of the study, the reactor model more suitable for treatment of this veterinary pharmaceutical effluent. In the second stage of the study, used a design factorial 24-1to optimize the variables of the process: pH, concentration of Fe2+ g/L, ozoniser power and output flow reactor. The efficiency of the treatment was evaluated by the reduction of Total Organic Carbon rate (TOC) (%). This study showed that the experimental condition in which it was observed the highest percentage of TOC reduction (46.14%) occurred when combined pH 4.0, [Fe 2 +] 0.5 g / L, the output flow reactor 1.23 L / h and ozoniser power of 56W. The statistical evaluation of this planning pointed to a new experimental setup in which we obtained 55.24% reduction of TOC, degradation of drug Fenbendazole 71.24% and degradation of 95.68% drug Triclabendazole. This new configuration combined pH 4.0, [Fe 2 +] of 0.1 g / L, output flow reactor of 1.85 L / h and ozoniser power of 56W.

No presente trabalho foi estudada a utilização do ozônio como auxiliar no pós-tratamento de reatores anaeróbios por reatores de lodos ativados. Foi estudada a influência da ozonização no aumento da biodegradabilidade da matéria orgânica recalcitrante de efluente anaeróbio antes de ser submetido ao tratamento aeróbio. A pesquisa foi dividida em três etapas. Na primeira e segunda etapas foram utilizados quatro amostras, uma bruta e três ozonizadas com dosagens de 5, 10 e 15 mg O3/L. As amostras da primeira e segunda etapa tiveram tempos de ozonização de 30 e 50 minutos, respectivamente. Os reatores de lodos ativados tiveram tempo de retenção celular de 10 dias e tempo de detenção hidráulica de 24 horas. Na terceira etapa foram utilizadas três amostras, uma bruta e duas ozonizadas cuja dosagem de ozônio foi de 15 mg/L, valor que obteve melhores resultados nas etapas anteriores. Os tempos de ozonização de cada amostra foram de 30 e 50 minutos. Nesta fase, o reator de lodos ativados teve tempo de retenção celular de 10 dias e tempo de detenção hidráulica de 12 horas. Entretanto, amostras ozonizadas submetidas a pós-tratamento em reator de lodos ativados, apresentaram aumento da biodegradabilidade quando expostas a maiores tempos de ozonização. A alimentação do reator de lodos ativados com amostras ozonizadas trouxe benefícios ao seu desempenho. / On this research was studied the utilization of ozone as auxiliary on the post-treatment of anaerobics reactors by activated sludges reactors. It was studied the influence of ozonization of anaerobic effluent before being submitted to an aerobic treatment on the increase of the biodegradability of recalcitrant organic matter. The research was divided in three stages. In the first and second stage was used four samples, one brute and three ozonizades with doses of 5, 10 and 15 mg O3/L. The samples used on first and second stages had being ozonization times of 30 and 50 minutes, respectively. The activated sludges reactors had time of cellular retention of 10 days and hydraulic time of detention of 24 hours. On the third stage were used three samples, one brute and two ozonizades whose doses of ozone was of 15 mg/L, this value achieved the best results in the previous stages. The ozonizations times of each sample were of 30 and 50 minutes. On this stage the activated sludges reactors had time of cellular retention of 10 days and hydraulic time of detention of 12 hours. It was observed that ozonizades samples submitted to post-treatment in activated sludges reactors presented increase of the biodegradability when exposed at largest times of ozonization. The feeding of activated sludges reactors with ozonizades samples benefit its perfomance.

Thesis (Msc Food Sc (Food Science))--University of Stellenbosch, 2007. / The distillery industry generates large volumes of heavily polluted wastewater and thus effective wastewater treatment is essential. It has been reported that a chemical oxygen demand (COD) reduction of more than 90% can be achieved when wine distillery wastewater (WDWW) is treated in an upflow anaerobic sludge blanket (UASB) reactor. The first objective of this study was to investigate UASB treatment of WDWW and to try to enhance the efficiency by using ozonation treatments. Secondly, the impact of grain distillery wastewater (GDWW) on UASB granules was determined. The third objective was to determine whether ozonation and enzymatic treatment combinations might improve the biodegradability of GDWW and thus make GDWW more amenable to UASB treatment. It was found that UASB treatment combined with ozonation improved the WDWW treatment efficiency. When diluted WDWW (chemical oxygen demand COD = 4 000 mg.L-1) was ozonated (dose = 47 mg.L-1) in a 50 L venturi circulating contactor system, the COD reduction was 7%. When WDWW was treated in a laboratory-scale UASB reactor (substrate pH = 7.0, COD = 4 000 mg.L-1 and organic loading rate (OLR) = 4.0 kg COD.m-3.d-1), the COD reduction was 92%. When the UASB treatment was combined with either pre- or postozonation, the COD reduction was 94 and 96%, respectively. When UASB treatment was combined with pre- and post-ozonation, a COD reduction of 98% was achieved. The activity of the UASB granules was also found to improve over time, despite the addition of the ozonation treatment. It has been reported that operational problems occur when GDWW is treated in an UASB reactor as a result of the encapsulation of the granules. This was confirmed when granules from a full-scale UASB treating WDWW became encapsulated in a layer after being exposed to GDWW (COD = 4 000 mg.L-1) for 24 d. The results showed that the lipid content of the granules increased from 1.25 to 60.35 mg lipid.g-1 granule over the 24 d exposure period. Therefore, granules exposed to GDWW were encapsulated in a lipid-rich layer and as a result the contact between the GDWW and microbial consortium in the granules was reduced. The operational problems found during the industrial UASB treatment of GDWW were ascribed to the encapsulation of the granules. Combinations of ozonation (dose = 1 476 mg.L-1) generated in a 2 L bubble column and enzymatic treatments (1% FogFreeTM (FF) dosage and 2 d incubation at 35°C) were found to improve the biodegradability of GDWW. This improvement was in terms of lipid reduction in GDWW, granule activity and visual appearance of the encapsulating layer of the granules. The highest lipid reduction (90%), highest granule activity, lowest lipid content of the granules (3.74 ± 0.10 mg.g-1 granule) and best visual appearance were achieved in ozonated GDWW treated with 1% FF, followed by just ozonation. The higher lipid reduction and subsequent higher granule activity were ascribed to the reduction in lipids which resulted in the fact that fewer lipids were available to encapsulate the granules. As a result of the lipid reduction, the granule activity improved and the GDWW was made more amenable to UASB treatment. This study proved that UASB treatment combined with ozonation led to an enhancement of the treatment efficiency of WDWW. It was also found that the cause of the operational problems during UASB treatment of GDWW was as a result of the granules being encapsulated in a lipid-rich layer. It was established that treating GDWW prior to UASB treatment improved the biodegradability of GDWW. The data from the study showed that high lipid reduction in the GDWW directly led to better granule activity, lower granule lipid content and a thinner encapsulating layer. Based on the data from this study, it is recommended that GDWW be ozonated prior to other treatments because it can be done inline and the costs would be lower than that of enzymatic treatments.