Desenvolvimento de um reator fotoquímico aplicável no tratamento de efluentes fenólicos presentes na indústria do petróleo

With water pollution increment at the last years, so many progresses in researches about treatment of contaminated waters have been developed. In wastewaters containing highly toxic organic compounds, which the biological treatment cannot be applied, the Advanced Oxidation Processes (AOP) is an alternative for degradation of nonbiodegradable and toxic organic substances, because theses processes are generation of hydroxyl radical based on, a highly reactivate substance, with ability to degradate practically all classes of organic compounds. In general, the AOP request use of special ultraviolet (UV) lamps into the reactors. These lamps present a high electric power demand, consisting one of the largest problems for the application of these processes in industrial scale. This work involves the development of a new photochemistry reactor composed of 12 low cost black light fluorescent lamps (SYLVANIA, black light, 40 W) as UV radiation source. The studied process was the photo-Fenton system, a combination of ferrous ions, hydrogen peroxide, and UV radiation, it has been employed for the degradation of a synthetic wastewater containing phenol as pollutant model, one of the main pollutants in the petroleum industry. Preliminary experiments were carrier on to estimate operational conditions of the reactor, besides the effects of the intensity of radiation source and lamp distribution into the reactor. Samples were collected during the experiments and analyzed for determining to dissolved organic carbon (DOC) content, using a TOC analyzer Shimadzu 5000A. The High Performance Liquid Chromatography (HPLC) was also used for identification of the cathecol and hydroquinone formed during the degradation process of the phenol. The actinometry indicated 9,06⋅1018 foton⋅s-1 of photons flow, for 12 actived lamps. A factorial experimental design was elaborated which it was possible to evaluate the influence of the reactants concentration (Fe2+ and H2O2) and to determine the most favorable experimental conditions ([Fe2+] = 1,6 mM and [H2O2] = 150,5 mM). It was verified the increase of ferrous ions concentration is favorable to process until reaching a limit when the increase of ferrous ions presents a negative effect. The H2O2 exhibited a positive effect, however, in high concentrations, reaching a maximum ratio degradation. The mathematical modeling of the process was accomplished using the artificial neural network technique

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitable surfactant was the EO 7 due to the lower reagent onsumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

Estudo da remoção de compostos orgânicos, benzeno e tolueno, em solução aquosa por processo oxidativo avançado do tipo Fenton

The oil and petrochemical industry is responsable to generate a large amount of waste and wastewater. Among some efluents, is possible find the benzene, toluene, ethilbenze and isomers of xilenes compounds, known as BTEX. These compounds are very volatily, toxic for environment and potencially cancerigenous in man. Oxidative advanced processes, OAP, are unconventional waste treatment, wich may be apply on treatment and remotion this compounds. Fenton is a type of OAPs, wich uses the Fenton s reactant, hydrogen peroxide and ferrous salt, to promove the organic degradation. While the Photo-Fenton type uses the Fenton s reactant plus UV radiation (ultraviolet). These two types of OAP, according to literature, may be apply on BTEX complex system. This project consists on the consideration of the utilization of technologies Fenton and Photo-Fenton in aqueous solution in concentration of 100 ppm of BTEX, each, on simulation of condition near of petrochemical effluents. Different reactors were used for each type of OAP. For the analyticals results of amount of remotion were used the SPME technique (solid phase microextraction) for extraction in gaseous phase of these analytes and the gas chromatography/mass espectrometry The arrangement mechanical of Photo-Fenton system has been shown big loss by volatilization of these compounds. The Fenton system has been shown capable of degradate benzene and toluene compounds, with massic percentage of remotion near the 99%.

Degradação do fungicida tiofanato metílico pelo processo foto-Fenton em reatores anular e solar

Effluents from pesticide industries have great difficulty to decontaminate the environment and, moreover, are characterized by high organic charge and toxicity. The research group Center for Chemical Systems Engineering (CESQ) at the Department of Chemical Engineering of Polytechnical School of University of São Paulo and Department of Chemical Engineering, Federal University of Rio Grande do Norte have been applying the Advanced Oxidation Processes (AOP's) for the degradation of various types of pollutants. These processes are based on the generation of hydroxyl radicals, highly reactive substances. Thus, this dissertation aims to explore this process, since it has been proven to be quite effective in removing organic charge. Therefore, it was decided by photo-Fenton process applied to the degradation of the fungicide Thiophanate methyl in aqueous system using annular reactor (with lamp Philips HPLN 125W) and solar. The samples were collected during the experiment and analyzed for dissolved organic carbon (TOC) using a Shimadzu TOC (Shimadzu 5050A e VCP). The Doehlert experimental design has been used to evaluate the influence of ultraviolet radiation, the concentrations of methyl thiophanate (C12H14N4O4S2), hydrogen peroxide (H2O2) and iron ions (Fe2+), among these parameters, was considered the best experimental conditions, [Fe2+] = 0.6 mmol/L and [H2O2] = 0.038 mol/L in EXP 5 experiment and in SOL 5 experiment, obtaining a percentage of TOC removal of 60% in the annular reactor and 75% in the solar reactor

Avaliação de diferentes processos oxidativos avançados no tratamento de resíduos de petróleo

The petroleum industry deals with problems which are difficult to solve because of their relation to environmental issues. This is because amounts of residue are generated which vary in type and danger level. The soil contamination by non aqueous liquid phase mixtures, specifically hydrocarbon petroleum has been a reason for great concern, mainly the aromatic and polycyclic aromatic, which present risk to human health due to its carcinogenic and mutagenic character. The Advanced Oxidative Processes (AOP) are efficient technologies for destruction of organic compounds of difficult degradation and, often, they are present in low concentrations. They can be considered clean technologies, because there is no formation of solid by-products or the transfer of pollutor phases. This work focuses on the study of the degradation of petroleum industrial waste, by Advanced Oxidation Processes. Treatments tackling petroleum residues, contaminated soil, and water occurring in the production of petroleum reached the following Polycyclic Aromatic Hydrocarbons (PAH) degradation levels: solid residues 100% in 96 treatment hours; water residue - 100% in 6 treatment hours; soil contamination (COT degradation) - 50.3% in 12 treatment hours. AOP were effective in dealing with petroleum residues thus revealing themselves to be a promising treatment alternative

Desenvolvimento de um sistema foto-oxidativo visando aplicação no tratamento de águas produzidas em campos de petróleo

Increasing concern with the environment, in addition to strict laws, has induced the industries to find altenatives to the treatment of their wastes. Actually, the oil industry has sought solutions to overcome a big environmental problem, i.e., oil field produced water being discharged to the sea. These effluents have organic compounds dissolved, such as polycyclic aromatic hydrocarbons, phenols, benzene, toluene, ethylbenzene and xylenes (BTEX). These compounds are difficult to be removed and have high toxicity. The advanced oxidation processes - AOP are effective to degradation of these organic compounds, because they generate hydroxyl radicals with high potential of oxidation. This work includes the reactor photochemical development applied in the photodegradation treatment (by photo-Fenton process) of wastewaters containing organic compounds dissolved, aiming at treatment and recovery the oil field produced water. The studied reactor allowed the evaluation of two ultraviolet radiation sources that is the main factor to describe the feasibility of the photo¬Fenton treatment, i.e., sun and black light fluorescent lamps, and other relevant variables the process: concentration of reagents, irradiated area and also various reactor configurations to maximize the use of radiation. The organic matter degradation was verified with samples collected during the experimental and analyzed with a total organic carbon analyzer (TOC), which expressed the results in terms of mgC/L. The solar radiation was more effective than radiation from the lamps. it's an important factor for the operation costs cutting. Preliminary experiments applied to oil field produced water treatment have showed satisfactory results, reducing up to 76 % of organic matter

Desenvolvimento de um sistema foto-oxidativo visando aplicação no tratamento de águas produzidas em campos de petróleo

Increasing concern with the environment, in addition to strict laws, has induced the industries to find alternatives to the treatment of their wastes. Actually, the oil industry has sought solutions to overcome a big environmental problem, i.e., oil field produced water being discharged to the sea. These effluents have organic compounds dissolved, such as polycyclic aromatic hydrocarbons, phenols, benzene, toluene, ethylbenzene and xylenes (BTEX). These compounds are difficult to be removed and have high toxicity. The advanced oxidation processes - AOP are effective to degradation of these organic compounds, because they generate hydroxyl radicals with high potential of oxidation. This work includes the reactor photochemical development applied in the photodegradation treatment (by photo-Fenton process) of wastewaters containing organic compounds dissolved, aiming at treatment and recovery the oil field produced water. The studied reactor allowed the evaluation of two ultraviolet radiation sources that is the main factor to describe the feasibility of the photo- Fenton treatment, i.e., sun and black light fluorescent lamps, and other relevant variables the process: concentration of reagents, irradiated area and also various reactor configurations to maximize the use of radiation. The organic matter degradation was verified with samples collected during the experimental and analyzed with a total organic carbon analyzer (TOC), which expressed the results in terms of mgC/L. The solar radiation was more effective than radiation from the lamps. It's an important factor for the operation costs cutting. Preliminary experiments applied to oil field produced water treatment have showed satisfactory results, reducing up to 76 % of organic matter

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitablesurfactant was the EO 7 due to the lower reagent consumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

Degradação eletroquímica de benzeno, tolueno e xileno via oxidação eletroquímica utilizando eletrodo Ti/Pt

This work is directed to the treatment of organic compounds present in produced water from oil using electrochemical technology. The water produced is a residue of the petroleum industry are difficult to treat , since this corresponds to 98 % effluent from the effluent generated in the exploration of oil and contains various compounds such as volatile hydrocarbons (benzene, toluene, ethylbenzene and xylene), polycyclic aromatic hydrocarbons (PAHs), phenols, carboxylic acids and inorganic compounds. There are several types of treatment methodologies that residue being studied, among which are the biological processes, advanced oxidation processes (AOPs), such as electrochemical treatments electrooxidation, electrocoagulation, electrocoagulation and eletroredution. The electrochemical method is a method of little environmental impact because instead of chemical reagents uses electron through reactions of oxide-reducing transforms toxic substances into substances with less environmental impact. Thus, this paper aims to study the electrochemical behavior and elimination of the BTX (benzene, toluene and xylene) using electrode of Ti/Pt. For the experiment an electrochemical batch system consists of a continuous source, anode Ti/Pt was used, applying three densities of current (1 mA/cm2, 2,5 mA/cm2 and 5 mA/cm2). The synthetic wastewater was prepared by a solution of benzene, toluene and xylene with a concentration of 5 ppm, to evaluate the electrochemical behavior by cyclic voltammetry and polarization curves, even before assessing the removal of these compounds in solution by electrochemical oxidation. The behavior of each of the compounds was evaluated by the use of electrochemical techniques indicate that each of the compounds when evaluated by cyclic voltammetry showed partial oxidation behavior via adsorption to the surface of the Ti/Pt electrode. The adsorption of each of the present compounds depends on the solution concentration but there is the strong adsorption of xylene. However, the removal was confirmed by UV-Vis, and analysis of total organic carbon (TOC), which showed a percentage of partial oxidation (19,8 % - 99,1 % TOC removed), confirming the electrochemical behavior already observed in voltammetry and cyclic polarization curves

Modelagem da degradação de fenol em efluentes aquosos através do processo de foto-fenton

Advanced Oxidation Processes (AOP) are techniques involving the formation of hydroxyl radical (HO•) with high organic matter oxidation rate. These processes application in industry have been increasing due to their capacity of degrading recalcitrant substances that cannot be completely removed by traditional processes of effluent treatment. In the present work, phenol degrading by photo-Fenton process based on addition of H2O2, Fe2+ and luminous radiation was studied. An experimental design was developed to analyze the effect of phenol, H2O2 and Fe2+ concentration on the fraction of total organic carbon (TOC) degraded. The experiments were performed in a batch photochemical parabolic reactor with 1.5 L of capacity. Samples of the reactional medium were collected at different reaction times and analyzed in a TOC measurement instrument from Shimadzu (TOC-VWP). The results showed a negative effect of phenol concentration and a positive effect of the two other variables in the TOC degraded fraction. A statistical analysis of the experimental design showed that the hydrogen peroxide concentration was the most influent variable in the TOC degraded fraction at 45 minutes and generated a model with R² = 0.82, which predicted the experimental data with low precision. The Visual Basic for Application (VBA) tool was used to generate a neural networks model and a photochemical database. The aforementioned model presented R² = 0.96 and precisely predicted the response data used for testing. The results found indicate the possible application of the developed tool for industry, mainly for its simplicity, low cost and easy access to the program.

Modelagem da degradação de fenol em efluentes aquosos através do processo de foto-fenton

Advanced Oxidation Processes (AOP) are techniques involving the formation of hydroxyl radical (HO•) with high organic matter oxidation rate. These processes application in industry have been increasing due to their capacity of degrading recalcitrant substances that cannot be completely removed by traditional processes of effluent treatment. In the present work, phenol degrading by photo-Fenton process based on addition of H2O2, Fe2+ and luminous radiation was studied. An experimental design was developed to analyze the effect of phenol, H2O2 and Fe2+ concentration on the fraction of total organic carbon (TOC) degraded. The experiments were performed in a batch photochemical parabolic reactor with 1.5 L of capacity. Samples of the reactional medium were collected at different reaction times and analyzed in a TOC measurement instrument from Shimadzu (TOC-VWP). The results showed a negative effect of phenol concentration and a positive effect of the two other variables in the TOC degraded fraction. A statistical analysis of the experimental design showed that the hydrogen peroxide concentration was the most influent variable in the TOC degraded fraction at 45 minutes and generated a model with R² = 0.82, which predicted the experimental data with low precision. The Visual Basic for Application (VBA) tool was used to generate a neural networks model and a photochemical database. The aforementioned model presented R² = 0.96 and precisely predicted the response data used for testing. The results found indicate the possible application of the developed tool for industry, mainly for its simplicity, low cost and easy access to the program.

Degradação foto-fenton de carbono orgânico total em efluentes da indústria de beneficiamento de castanha de caju

At the cashew nut processing industry it is often the generation of wastewaters containing high content of toxic organic compounds. The presence of these compounds is due mainly to the so called liquid of the cashew nut (CNSL). CNSL, as it is commercially known in Brazil, is the liquid of the cashew nut. It looks like an oil with dark brown color, viscous and presents a high toxicity index due to the chemical composition, i.e. phenol compounds, such as anacardic acid, cardol, 2-methyl cardol and monophenol (cardanol). These compounds are bio resistant to the conventional treatments. Furthermore, the corresponding wastewaters present high content of TOC (total organic carbon). Therefore due to the high degree of toxicity it is very important to study and develop treatments of these wastewaters before discharge to the environmental. This research aims to decompose these compounds using advanced oxidative processes (AOP) based on the photo-Fenton system. The advantage of this system is the fast and non-selective oxidation promoted by the hydroxyl radicals (●OH), that is under determined conditions can totally convert the organic pollutants to CO2 and H2O. In order to evaluate the decomposition of the organic charge system samples of the real wastewater od a processing cashew nut industry were taken. This industry was located at the country of the state of Rio Grande do Norte. The experiments were carried out with a photochemical annular reactor equipped with UV (ultra violet) lamp. Based on preliminary experiments, a Doehlert experimental design was defined to optimize the concentrations of H2O2 and Fe(II) with a total of 13 runs. The experimental conditions were set to pH equal to 3 and temperature of 30°C. The power of the lamps applied was 80W, 125W and 250W. To evaluate the decomposition rate measures of the TOC were accomplished during 4 hours of experiment. According to the results, the organic removal obtained in terms of TOC was 80% minimum and 95% maximum. Furthermore, it was gotten a minimum time of 49 minutes for the removal of 30% of the initial TOC. Based on the obtained experimental results, the photo-Fenton system presents a very satisfactory performance as a complementary treatment of the wastewater studied

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

Compósitos poliméricos a base de fibras de licuri: efeitos da hibridização e do envelhecimento ambiental acelerado

The gradual replacement of conventional materials by the ones called composite materials is becoming a concern about the response of these composites against adverse environmental conditions, such as ultraviolet radiation, high temperature and moist. Also the search for new composite using natural fibers or a blend of it with synthetic fibers as reinforcement has been studied. In this sense, this research begins with a thorough study of microstructural characterization of licuri fiber, as a proposal of alternative reinforcement to polymeric composites. Thus, a study about the development of two composite laminates was done. The first one, involving only the fiber of licuri and the second comprising a hybrid composite based of fiber glass E and the fiber of licuri, in order to know the performance of the fiber when of fiber across the hybridization process. The laminates were made in the form of plates using the tereftálica ortho-polyester resin as matrix. The composite laminate made only by licuri fiber had two reinforcing fabric layers of unidirectional licuri and the hybrid composite had two reinforcing layers of unidirectional licuri fabric and three layers of fiber short glass-E mat. Finally, both laminates was exposed to aging acceleration in order to study the influence of environmental degradation involving the mechanical properties and fracture characteristics thereof. Regarding the mechanical properties of composites, these were determined through uniaxial tensile tests, uniaxial compression and three bending points for both laminates in original state, and uniaxial tensile tests and three bending points after accelerated aging. As regards the study of structural degradation due to aging of the laminates, it was carried out based on microscopic analysis and microstructure, as well as measuring weight loss. The characteristics of the fracture was performed by macroscopic and microscopic (optical and SEM) analysis. In general, the laminated composites based on fiber licuri showed some advantages in their responses to environmental aging. These advantages are observed in the behavior related to stiffness as well as the microstructural degradation and photo-oxidation processes. However, the structural integrity of this laminate was more affected in case the action of uniaxial tensile loads, where it was noted a lower rate of withholding his last resistance property

Síntese e caracterização de CuNb2O6 e CuNbC através de reação sólido- sólido e gás- sólido a baixa temperatura

The refractory metal carbides have proven important in the development of engineering materials due to their properties such as high hardness, high melting point, high thermal conductivity and high chemical stability. The niobium carbide presents these characteristics. The compounds of niobium impregnated with copper also have excellent dielectric and magnetic properties, and furthermore, the Cu doping increases the catalytic activity in the oxidation processes of hydrogen. This study aimed to the synthesis of nanostructured materials CuNbC and niobium and copper oxide from precursor tris(oxalate) oxiniobate ammonium hydrate through gas-solid and solid-solid reaction, respectively. Both reactions were carried out at low temperature (1000°C) and short reaction time (2 hours). The niobium carbide was produced with 5 % and 11% of copper, and the niobium oxide with 5% of copper. The materials were characterized by X-Ray Diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), X-Ray Fluorescence Spectroscopy (XRF), infrared spectroscopy (IR), thermogravimetric (TG) and differential thermal analysis (DTA , BET and particle size Laser. From the XRD analysis and Rietveld refinement of CuNbC with S = 1.23, we observed the formation of niobium carbide and metallic copper with cubic structure. For the synthesis of mixed oxide made of niobium and copper, the formation of two distinct phases was observed: CuNb2O6 and Nb2O5, although the latter was present in small amounts