Estudo de métodos de tratamento de efluentes (troca iônica e eletroquímico) separados e sequenciais para eliminação de derivados de petróleo

The produce of waste and the amount of the water produced coming from activities of petroleum production and extraction has been a biggest challenge for oil companies with respect to environmental compliance due to toxicity. The discard or the reuse this effluent containing organic compounds as BTEX (benzene, toluene, ethylbenzene and xylene) can cause serious environmental and human health problems. Thus, the objective this paper was study the performance of two process (separately and sequential) in one synthetic effluent for the benzene, toluene and xylene removal (volatile hydrocarbons presents in the produced water) through of electrochemical treatment using Ti/Pt electrode and exchange resin ionic used in the adsorption process. The synthetic solution of BTX was prepared with concentration of 22,8 mg L-1, 9,7 mg L-1 e 9,0 mg L-1, respectively, in Na2SO4 0,1 mol L-1. The experiments was developed in batch with 0.3 L of solution at 25ºC. The electrochemical oxidation process was accomplished with a Ti/Pt electrode with different current density (J = 10, 20 e 30 mA.cm-2). In the adsorption process, we used an ionic exchange resin (Purolite MB 478), using different amounts of mass (2,5, 5 and 10 g). To verify the process of technics in the sequential treatment, was fixed the current density at 10 mA cm-2 and the resin weight was 2.5 g. Analysis of UV-VIS spectrophotometry, chemical oxygen demand (COD) and gas chromatography with selective photoionization detector (PID) and flame ionization (FID), confirmed the high efficiency in the removal of organic compounds after treatment. It was found that the electrochemical process (separate and sequential) is more efficient than absorption, reaching values of COD removal exceeding 70%, confirmed by the study of the cyclic voltammetry and polarization curves. While the adsorption (separately), the COD removal did not exceed 25,8%, due to interactions resin. However, the sequential process (electrochemical oxidation and adsorption) proved to be a suitable alternative, efficient and cost-effectiveness for the treatment of effluents petrochemical.

Aplicação da oxidação eletroquímica no tratamento de efluentes contendo corantes reativos utilizando Ti/Pt e Ti/Pt-SnSb

The textile effluents are a complex mixture of many pollutants that contain high organic loads, severe color and toxic compounds. The high concentration of the textile effluent may cause increased chemical demand (COD) and biochemical (BOD) of oxygen, elevated temperature, acidity or alkalinity, causing damage and environmental problems. In addition to representing a serious threat to human health such effluent is also quite toxic to most aquatic organisms. And for this reason, one must meet the concentration limits for emission sources and sewage system. This study aimed to investigate the performance of electrochemical treatment of a textile effluent for the removal of color, turbidity, dissolved oxygen (DO) and dissolved organic matter by investigating the influence of experimental parameters such as the electrocatalyst materials (Ti/Pt and Ti/Pt-SnSb) and current density in order to compare their efficiency, energy consumption and cost. The dye Novacron Blue CD (NB) was employed in synthetic solution, while the dyes Remazol Yellow 3RS (RY 3RS) Remazol Red RR Gran (RR-RR Gran) and Navy Blue CL-R (NB CL-R) were used to generate simulated textile effluent laboratory. The results showed that the application of electrochemical oxidation process favors the elimination of color effectively independent the electrocatalytic material and current used, as well as treated effluent. However, the influence of electrocatalytic material was crucial to reduction of the organic matter in all cases.

Estudo comparativo dos processos eletroquímicos oxidativos avançados (PEOAs) no tratamento de efluentes contendo corantes orgânicos de difícil degradação

Organic dyes have been widely used in various branches of dyeing industries. These compounds are known to be very toxic, mutagenic, cancinogenic only cause aesthetic pollution and irreversible damage to aquatic ecosystems and human health. Are recalcitrant contaminants due to its high stability and resistance to photobleaching and bio. Given this context, the search for technologies that can minimize the effects of such pollutants is required. In recent decades the Electrochemical Oxidation Process Advanced (PEOAs) based on the generation of strongly oxidizing species (radicals ●OH) offer promising approaches for the prevention of problems caused by industrial effluents. This study analyzed the degradation and mineralization of textile dyes and the study of a real effluent in order to assess the feasibility of PEOAs: Electro-Fenton (EF), Photo Electro-Fenton (PEF) and anodic oxidation (AO), and these methods still was studied the Solar Fotoelectro-Fenton (SPEF) in a pre-pilot plant, in order to study the electrochemical treatment on an industrial scale. In the study has compared the effect of PEOAs in the removal of color, TOC and decay kinetics of degradation of the compounds, and also for using the Congo Red (CR) SPEF studies were performed mineralization current efficiency (MCE). The best results are given to the treatment of the PEF for all the studied dyes. From the results it was possible to choose the PEF as the most effective and promising for application of treatment when compared to other methods of treatment, and prove from SPEF that the process can be used in industrial scales, since this method PEF has been improved and solar irradiation replaced the UVA lamp.

Estudo comparativo dos processos eletroquímicos oxidativos avançados (PEOAs) no tratamento de efluentes contendo corantes orgânicos de difícil degradação

Organic dyes have been widely used in various branches of dyeing industries. These compounds are known to be very toxic, mutagenic, cancinogenic only cause aesthetic pollution and irreversible damage to aquatic ecosystems and human health. Are recalcitrant contaminants due to its high stability and resistance to photobleaching and bio. Given this context, the search for technologies that can minimize the effects of such pollutants is required. In recent decades the Electrochemical Oxidation Process Advanced (PEOAs) based on the generation of strongly oxidizing species (radicals ●OH) offer promising approaches for the prevention of problems caused by industrial effluents. This study analyzed the degradation and mineralization of textile dyes and the study of a real effluent in order to assess the feasibility of PEOAs: Electro-Fenton (EF), Photo Electro-Fenton (PEF) and anodic oxidation (AO), and these methods still was studied the Solar Fotoelectro-Fenton (SPEF) in a pre-pilot plant, in order to study the electrochemical treatment on an industrial scale. In the study has compared the effect of PEOAs in the removal of color, TOC and decay kinetics of degradation of the compounds, and also for using the Congo Red (CR) SPEF studies were performed mineralization current efficiency (MCE). The best results are given to the treatment of the PEF for all the studied dyes. From the results it was possible to choose the PEF as the most effective and promising for application of treatment when compared to other methods of treatment, and prove from SPEF that the process can be used in industrial scales, since this method PEF has been improved and solar irradiation replaced the UVA lamp.

Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Uso de reator seqüencial em batelada (RSB) para pós-tratamento de efluente de reator anaeróbio

Este trabalho consistiu no pós-tratamento de efluente de reator anaeróbio, em um sistema de reator seqüencial em batelada (RSB), com vistas à remoção biológica de nitrogênio e fósforo. Primeiramente, em escala de laboratório, verificou-se a eficiência de três RSBs, com ciclos operacionais diferenciados, tratando o efluente produzido por um reator seqüencial em batelada anaeróbio (RSBAn), alimentado por esgoto sintético, caracteristicamente doméstico. Neste experimento, também acoplou-se um sistema de aquisição de dados aos RSBs, para monitorar continuamente os parâmetros pH, redox e OD, com o objetivo de obter pontos inferenciais de controle dos processos de nitrificação, desnitrificação e remoção biológica de fósforo. Subseqüente a este experimento, desenvolveu-se um sistema de RSB em escala piloto, tratando o efluente anaeróbio real de um UASB (Upflow Anaerobic Sludge Blanket), no intuito de analisar o efeito da mudança de escala e do tipo de esgoto, que passou de sintético a real, na performance do RSB. No experimento em escala de laboratório, os resultados obtidos demonstraram boas eficiências de remoção de DQO e SS, e uma ótima eficiência no processo de nitrificação. As eficiências médias de remoção de DQO, SS e nitrificação, foram respectivamente de 93,3%, 90,7% e 98,9%. O processo de desnitrificação não desenvolveu-se satisfatoriamente devido às baixas concentrações de matéria orgânica do efluente anaeróbio. O processo de remoção biológica de fósforo, além das baixas DQO afluentes, foi prejudicado pelas idades de lodo extremamente longas estabelecidas nesta fase experimental, em função da aplicação da estratégia de controle de processo baseada na concentração de SSV no licor. Objetivando-se aumentar a concentração de matéria orgânica imediatamente disponível no afluente, com o conseqüente acréscimo de eficiência nos processos de desnitrificação e remoção biológica de fósforo, introduziu-se um pré-fermentador, para gerar metade do efluente anaeróbio a ser tratado nos RSBs. O controle do processo passou a ser efetuado através da aplicação de uma idade de lodo pré-estabelecida de 20 dias. Observou-se um aumento bastante significativo do processo de desnitrificação, atingindo uma eficiência da ordem de 70,4%. No entanto, as maiores concentrações de matéria orgânica solúvel, com a introdução do pré-fermentador, não foram suficientes para estimular o desenvolvimento das bactérias removedoras de fósforo. Um aumento de DQO do esgoto sintético foi necessário para permitir a simultaneidade dos processos de desnitrificação e remoção de fósforo. Porém, apesar de apresentar ciclos operacionais com eficiências de 100% de remoção de fósforo, este processo não mostrou-se confiável, alternando entre fases de boas, médias e más eficiências. Provavelmente as idades de lodo, ainda muito altas para promover a remoção de fósforo do sistema, justificam a permanência bastante irregular na eficiência deste processo. Neste período, a concentração média de DQO necessária para atingir-se uma eficiência satisfatória nos processos conjuntos de nitrificação e desnitrificação, foi de 644,6 mg/L. As seguintes eficiências foram observadas: 95,8% na remoção de DQO, 98,7% na nitrificação, 76,8% na desnitrificação e 74,5% na remoção de nitrogênio. O acompanhamento "on line" de pH, redox e OD mostrou-se como uma eficiente ferramenta inferencial no controle de processos biológicos, principalmente daqueles referentes à remoção de nitrogênio. Dentre os três parâmetros monitorados, o pH apresentouse como o mais representativo. No experimento em escala piloto, o processo de nitrificação não desenvolveu-se possivelmente devido ao efeito conjunto de baixos tempos de detenção nas etapas aeróbias dos ciclos operacionais dos RSBs, com a ação tóxica de sulfetos produzidos no tratamento anaeróbio. O processo de remoção biológica de fósforo, similarmente ao experimento em escala de bancada, não mostrou-se confiável, apresentando períodos alternados de eficiência. Por fim, com vistas a verificar o desenvolvimento de processo inibitório por efluentes de tratamento anaeróbio em sistemas aeróbios, realizou-se uma série de testes de inibição com o efluente anaeróbio e também especificamente com sulfeto. Os testes respirométricos (DBO última e em batelada), foram de essencial importância para analisar a tratabilidade biológica de esgoto contendo composto tóxico. Pôde-se comprovar que o sulfeto, presente no efluente anaeróbio real, ou o efeito de sua combinação com outras substâncias contidas no lodo ativado, alterou a cinética dos processos biológicos desenvolvidos no sistema de tratamento do tipo lodo ativado.

Estudo de técnicas para o tratamento alternativo de efluentes oleosos oriundos da industrialização da castanha de caju

An evaluation project was conducted on the technique of treatment for effluent oil which is the deriving process to improve cashews. During the evaluation the following techniques were developed: advanced processes of humid oxidation, oxidative processes, processes of biological treatment and processes of adsorption. The assays had been carried through in kinetic models, with an evaluation of the quality of the process by means of determining the chemical demand of oxygen (defined as a technique of control by means of comparative study between the available techniques). The results demonstrated that the natural biodegradation of the effluent ones is limited, as result using the present natural flora in the effluent one revealed impracticable for an application in the industrial systems, independent of the evaluation environment (with or without the oxygen presence). The job of specific microorganisms for the oily composite degradation developed the viability technique of this route, the acceptable levels of inclusion in effluent system of treatment of the improvement of the cashew being highly good with reasonable levels of removal of CDO. However, the use combined with other techniques of daily pay-treatment for these effluent ones revealed to still be more efficient for the context of the treatment of effluent and discarding in receiving bodies in acceptable standards for resolution CONAMA 357/2005. While the significant generation of solid residues the process of adsorption with agroindustrial residues (in special the chitosan) is a technical viable alternative, however, when applied only for the treatment of the effluent ones for discarding in bodies of water, the economic viability is harmed and minimized ambient profits. Though, it was proven that if used for ends of I reuse, the viability is equalized and justifies the investments. There was a study of the photochemistry process which have are applicable to the treatment of the effluent ones, having resulted more satisfactory than those gotten for the UV-Peroxide techniques. There was different result on the one waited for the use of catalyses used in the process of Photo. The catalyses contained the mixing oxide base of Cerium and Manganese, incorporated of Potassium promoters this had presented the best results in the decomposition of the involved pollutants. Having itself an agreed form the gotten photochemistry daily paytreatment resulted, then after disinfection with chlorine the characteristics next the portability to the water were guarantee. The job of the humid oxidation presented significant results in the removal of pollutants; however, its high cost alone is made possible for job in projects of reuses, areas of low scarcity and of raised costs with the capitation/acquisition of the water, in special, for use for industrial and potable use. The route with better economic conditions and techniques for the job in the treatment of the effluent ones of the improvement of the cashew possesses the sequence to follow: conventional process of separation water-oil, photochemistry process and finally, the complementary biological treatment

Tecnologia eletroquímica como tratamento alternativo de efluentes têxteis sintéticos utilizando ânodos de platina e diamante

In this work, the treatment of synthetic wastewaters containing Remazol Red BR (RRB) and Novacron Blue C-D (NB) by anodic oxidation using boron doped diamond anodes (BDD) and Novacron Yellow (YN) using BDD and Platinum (Pt) anodes was investigated. Galvanostatic electrolyses of RRB and NB synthetic wastewaters have led to the complete decolorization removal at different operating conditions (current density, pH and temperature). The influence of these parameters was investigated in order to find the best conditions for dyestuff colour removal. According to the experimental results obtained, the electrochemical oxidation process is suitable for decolorizing wastewaters containing these textile dyes, due to the electrocatalytic properties of BDD and Pt anode. Energy requirements for removing colour during galvanostatic electrolyses of RRB, NB and YN synthetic solutions depends mainly on the operating conditions; for example for RRB, it passes from 3.30 kWh m-3 at 20 mA cm-2 to 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH = 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (data estimated per volume of treated effluent). In order to verify the Brazilian law regulations of NB and RRB synthetic solutions after electrochemical decolourisation treatment, Hazen Units values were determined and the total colour removal was achieved; remaining into the regulations. Finally, electrical energy cost for removing colour was estimated

Estudo de dinâmicas populacionais aplicado a processos de tratamento biológico de efluentes

The purpose of this work is to perform studies of mathematical modeling of the relationship of interaction occurring between microrganisms participants from wastewater treatment processes aimed at understanding, through simulations, such as inter-relationships can affect the performance of such units. The methodology was the implementation in FORTRAN computer language of mathematical models of microbial interactions. The first model addresses the interaction of bacteria-forming flakes and filamentous bacteria in activated sludge systems, which seeks to strike a balance between these bacteria to improve efficiency of the process. Another model is studied the interaction between bacteria and protozoa in activated sludge systems and analyzing the efficiency of the process, observing the changes in daily load. Microbial interactions in anaerobic reactors were dealt a third model, in which there is the mutualistic interaction between acidogenic and methanogenic bacteria. In a fourth and final model was examined the relationship between the bacteria Acinetobacter sp. and Gordonia sp., which are present in activated sludge systems, showing the competitive capacity of Acinetobacter sp. can control the growth of unwanted bacteria.

Degradação dos fármacos ciprofloxacino e sertalina pelos processos ferro zero e foto-Fenton - aplicação em amostras de efluentes de estação de tratamento de esgoto

Pós-graduação em Química - IQ

Pós-tratamento físico-químico por flotação de efluentes de reatores anaeróbios de manta de lodo (UASB)

O emprego da flotação por ar dissolvido (FAD) para o pós-tratamento de efluentes de reatores anaeróbios aparenta ser atraente considerando algumas características desse processo físico-químico. A FAD é reconhecidamente um processo de alta taxa, particularmente eficiente na remoção de material particulado em suspensão e de flocos produzidos pela coagulação química de águas residuárias. Além disso, há produção de lodo espesso e provavelmente arraste de parcela de gases e de compostos voláteis, presentes nos efluentes anaeróbios. Entretanto, a concepção de sistemas de FAD deve ser precedida por ensaios em unidades de flotação em escala de laboratório, permitindo a determinação dos principais parâmetros do processo. Neste trabalho, são apresentados e discutidos os resultados obtidos em laboratório e em instalação piloto de flotação com escoamento contínuo recebendo efluente de reator anaeróbio de manta de lodo (UASB), com 18 m3 de volume, tratando esgoto sanitário. Os ensaios em unidade em escala de laboratório foram realizados utilizando diferentes dosagens de cloreto férrico (entre 30 e 110 mg/L) ou de polímero catiônico (entre 1,0 e 16,0 mg/L), atuando como coagulantes. Além disso, foram estudadas as condições de floculação (tempo de 15 e de 25 min, e gradiente médio de velocidade de floculação entre 30 e 100 s-1) e diferentes valores de quantidade de ar fornecido ao processo (S*, entre 4,7 e 28,5 g de ar por m3 de efluente). Com a instalação piloto de FAD foram realizados apenas ensaios preliminares variando-se a taxa de aplicação superficial (140 e 210 m3/m2/d) para diferentes valores de S* (14,8 a 29,5 g de ar por m3 de efluente). Com o emprego de dosagem de 65 mg/L de cloreto férrico, de tempo de 15 min e gradiente médio de velocidade de floculação de 80 s-1 e de 19 g de ar por m3 de efluente, foram observados excelentes resultados em laboratório, com elevadas remoções de DQO (89%), de fosfato total (96%), de sólidos suspensos totais (96%), de turbidez (98%), de cor aparente (91%), de sulfetos (não detectado) e NTK (47%). Considerando o sistema UASB e FAD, nos testes em laboratório, foram observadas remoções globais de 97,7% de DQO, de 98,0% de fosfato total, de 98,9% de SST, de 99,5% de turbidez, de 97,8% de cor aparente e de 59,0% de NTK. Nos ensaios com a instalação piloto de FAD, o sistema apresentou remoções de 93,6% de DQO, de 87,1% de SST, de 90% de sulfetos e de 30% de NTK.

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.