Tratamento de materiais contaminados com bifenilas policloradas (PCBS) via extração convencional e fluído supercrítico

The decontamination of the materials has been subject of some studies. One of the factors that it increases the pollution is the lack of responsibility in the discarding of toxic trash, as for example the presence of PCB (Polychlorinated Biphenyls) in the environment. In the Brazilian regulations, the material contaminated with PCB in concentrations higher than 50 ppm must be stored in special places or destroyed, usually by incineration in plasma furnace with dual steps. Due to high cost of the procedure, new methodologies of PCBs removal has been studied. The objective of this study was to develop an experimental methodology and analytical methodology for quantification of removal of PCBs through out the processes of extractions using supercritical fluid and Soxhlet method, also technical efficiency of the two processes of extraction, in the treatment of contaminated materials with PCBs. The materials studied were soils and wood, both were simulated contamination with concentration of 6.000, 33.000 and 60.000 mg of PCB/ kg of materials. Soxhlet extractions were performed using 100 ml of hexane, and temperature of 180 ºC. Extractions by fluid supercritical were performed at conditions of 200 bar, 70°C, and supercritical CO2 flow-rate of 3 g/min for 1-3 hours. The extracts obtained were quantified using Gas chromatography-mass spectrometry (GC/MS). The conventional extractions were made according to factorial experimental planning technique 22, with aim of study the influence of two variables of process extraction for the Soxhlet method: contaminant concentration and extraction time for obtain a maximum removal of PCB in the materials. The extractions for Soxhlet method were efficient for extraction of PCBs in soil and wood in both solvent studied (hexane and ethanol). In the experimental extraction in soils, the better efficient of removal of PCBs using ethanol as solvent was 81.3% than 95% for the extraction using hexane as solvent, for equal time of extraction. The results of the extraction with wood showed statistically it that there is not difference between the extractions in both solvent studied. The supercritical fluid extraction in the conditions studied showed better efficiency in the extraction of PCBs in the wood matrix than in soil, for two hours extractions the obtain percentual of 43.9 ± 0.5 % for the total of PCBs extracted in the soils against 95.1 ± 0,5% for the total of PCBs extracted in the wood. The results demonstrated that the extractions were satisfactory for both technical studied

Remoção conjugada de metais e óleo de água produzida

Petroleum can be associated or not with natural gas, but in both cases water is always present in its formation. The presence of water causes several problems, such as the difficulty of removing the petroleum from the reservoir rock and the formation of waterin-oil and oil-in-water emulsions. The produced water causes environmental problems, which should be solved to reduce the effect of petroleum industry in the environment. The main objective of this work is to remove simultaneously from the produced water the dispersed petroleum and dissolved metals. The process is made possible through the use of anionic surfactants that with its hydrophilic heads interacts with ionized metals and with its lipophilic tails interacts with the oil. The studied metals were: calcium, magnesium, barium, and cadmium. The surfactants used in this research were derived from: soy oil, sunflower oil, coconut oil, and a soap obtained from a mixture of 5wt.% coconut oil and 95wt.% animal fat. It was used a sample of produced water from Terminal de São Sebastião, São Paulo. As the concentration of the studied metals in produced water presented values close to 300 mg/L, it was decided to use this concentration as reference for the development of this research. Molecular absorption and atomic absorption spectroscopy were used to determine petroleum and metals concentrations in the water sample, respectively. A constant pressure filtration system was used to promote the separation of solid and liquid phases. To represent the behavior of the studied systems it was developed an equilibrium model and a mathematical one. The obtained results showed that all used surfactants presented similar behavior with relation to metals extraction, being selected the surfactant derived from soy oil for this purpose. The values of the partition coefficients between the solid and liquid phases " D " for the studied metals varied from 0.2 to 1.1, while the coefficients for equilibrium model " K " varied from 0.0002 and 0.0009. The removal percentile for oil with all metals associated was near 100%, showing the efficiency of the process

Extração de ferro da cera de carnaúba utilizando sistemas microemulsionados

The constant search for biodegradable materials for applications in several fields shows that carnauba wax can be a viable alternative in the manufacturing of biolubricants. Carnauba wax is the unique among the natural waxes to have a combination of properties of great importance. In previous studies it was verified the presence of metals in wax composition that can harm the oxidative stability of lubricants. Considering these factors, it was decided to develop a research to evaluate iron removal from carnauba wax, using microemulsion systems (Me) and perform the optimization of parameters, such as: extraction pH, temperature, extraction time, among others. Iron concentration was determined by atomic absorption and, to perform this analysis, sample digestion in microwave oven was used, showing that this process was very efficient. It was performed some analysis in order to characterize the wax sample, such as: attenuated total reflectance infrared spectroscopy (ATR-IR), thermogravimetry (TG), differential scanning calorimetry (DSC), energy dispersive X-ray fluorescence (EDXRF), scanning electron microscopy (SEM) and melting point (FP). The microemulsion systems were composed by: coconut oil as surfactant, n-butanol as cosurfactant, kerosene and/or heptanes as oil phase, distilled water as water phase. The pH chosen for this study was 4.5 and the metal extraction was performed in finite experiments. To evaluate Me extraction it was performed a factorial design for systems with heptane and kerosene as oil phase, also investigating the influence of temperature time and wax/Me ratio, that showed an statistically significant answer for iron extraction at 95% confidence level. The best result was obtained at 60°C, 10 hours contact time and 1: 10 wax/Me ratio, in both systems with kerosene and heptanes as oil phase. The best extraction occurred with kerosene as oil phase, with 54% iron removal

Extração de metais pesados de efluentes da indústria do petróleo utilizando derivados de óleos vegetais como extratantes

The study of a promising alternative for the treatment of produced water from the oil industry envisaging its reuse was the focus of this work. Millions of liters of water are generated per day, containing heavy metals in low concentrations (< 0,15 mg/L for Pb, <0,04 mg/L for Cd, <0,04 mg/L for Ni). The technology applied to extract these metals from aqueous phase was the solvent extraction and the extratants used were vegetable oils originated from coconut oil. They can be used in natural form or as derivatives, known as MAC - Mixture of Carboxílics Acids. The determination of the heavy metal con¬centrations in a complex matrix was made by using the atomic absorption spectrometry technique (AAS). On the bench tests using synthetics aqueous solutions containing metals, vegetable oils showed no power to extract the metals studied. The extractant MAC was selective for the Pb> Cd> Ni, in the concentration of 8% in the same organic phase. In this condition, the lower efficiency of extraction obtained was 92% for the Pb, 69% for the Cd, in the range of pH ranging from 6 to 8. An experimental planning was conducted for continuous tests. The device used was called MDIF Misturador-Decantador à Inversão de Fases and the aqueous phase was produced water from Pólo Indutrial de Guamaré/RN . No correlation between the studied variables (concentration of metal, concentration of extratant and agitation in the mixing chamer) could be obtained, because of possible factors which occurred as: variation in the composition of the studied sample, phenomena of precipitation and complexation of metals in the reservoir of feed, solubility of extratant

Comparação entre planejamento estatístico experimental e análise dimensional em operações de mistura e separação para sistema óleo-água

This work aims to determine a better methodology to help predicting some operational parameters to a new design of mixer-settler on treating wastewater produced by petroleum industry, called MDIF (Misturador-Decantador à Inversão de Fases/ Mixer-Settler based on Phase Inversion MSPI). The data from this research were obtained from the wastewater treatment unit, called MSPI-TU, installed on a wastewater treatment plant (WTP) of PETROBRAS/UO-RNCE. The importance in determining the better methodology to predict the results of separation and extraction efficiency of the equipment, contributes significantly to determine the optimum operating variables for the control of the unit. The study was based on a comparison among the experimental efficiency (E) obtained by operating MSPI-TU, the efficiency obtained by experimental design equation (Eplan) from the software Statistica Experimental Design® (version 7.0), and the other obtained from a modeling equation based on a dimensional analysis (Ecalc). The results shows that the experimental design equation gives a good prediction of the unit efficiencies with better data reliability, regarding to the condition before a run operation. The average deviation between the proposed by statistic planning model equation and experimental data was 0.13%. On the other hand, the efficiency calculated by the equation which represents the dimensional analysis, may result on important relative deviations (up 70%). Thus, the experimental design is confirmed as a reliable tool, with regard the experimental data processing of the MSPI-TU

Estudo da influência de tensoativos em sistemas microemulsionados na extração de gálio e alumínio

Gallium is an important material used in the electronic industry whose demand in the world market is increasing in view of its potential applications. A selective technique is required to allow for the production of the metal, separated from aluminium. Due to the fact that microemulsions constitute an attractive alternative to metal extraction procedures, microemulsified systems have been employed as gallium-selective extraction agents. Two surfactants have been synthesized: sodium 12-N,N-diethylamino-9,10-dihydroxyestearate (AMINE) and saponified coconut oil (SCO), both produced from raw materials readily available in Northeastern Brazil. Also, the commercial extraction agent KELEX-100, conventionally used with the same purpose, has been used in this work for comparison. The optimization of the extraction process with microemulsions was carried out by investigating the influence of some parameters, namely the type of cosurfactant, the cosurfactant/surfactant (C/S) ratio, the pH and concentration of metals in the aqueous phase. Pseudoternary diagrams, which are representative of the microemulsified systems under study, have been constructed in order to establish the boundaries of the regions where the several Winsor systems are formed. An experimental planning methodology (Scheffé Net) has been used to optimize the extraction. The extraction percentage values were as high as 100% for gallium and 99.99% for aluminium for the system with KELEX-100; 96.6% for gallium and 98.8% for aluminium for the system containing AMINE; and 88% for gallium and 85% for aluminium for the system with SCO. The microemulsified system chosen for presenting the best results in gallium extraction was composed by SCO/isoamyl alcohol/kerosene/Bayer licquor with a C/S ratio of 28 and pH of the original aqueous phase of 6.0. The selectivity that has not been observed in the extraction stage was accomplished in the reextraction process using HCl. For the KELEX-100 system, gallium was reextracted at 100% with 6M HCl and aluminium was reextracted at 100% with 0.8M HCl. For the AMINE system, the reextraction percentages were also 100% for both metals, using 6M HCl for gallium and 0.5M HCl for aluminium. On the other hand, the reextraction percentages for the system with SCO were as high as 84% for gallium and 92% for aluminium, with HCl in the same concentrations as those used in the AMINE system. Finally, an optimized system was applied in the gallium extraction process employing a reciprocating perforated-plates extractor. As a result, the metal content was extracted at a recovery rate of 95% for gallium and 97% for aluminium

Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões

The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market

Estudo da digestão de sedimento de curtume visando a extração do cromo por microemulsão

Leather tanneries generate effluents with high content of heavy metals, especially chromium, which is used in the mineral tanning process. Microemulsions have been studied in the extraction of heavy metals from aqueous solutions. Considering the problems related with the sediment resulting from the tanning process, due to its high content in chromium, in this work this sediment was characterized and microemulsion systems were applied for chromium removal. The extraction process consists in the removal of heavy metal ions present in an aqueous feeding solution (acid digestion solution) by a microemulsion system. First three different solid sludge digestion methods were evaluated, being chosen the method with higher digestion capacity. For this digestion method, seeking its optimization, was evaluated the influence of granule size, temperature and digestion time. Experimental results showed that the method proposed by USEPA (Method A) was the most efficient one, being obtained 95.77% of sample digestion. Regarding to the evaluated parameters, the best results were achieved at 95°C, 14 Mesh granule size, and 60 minutes digestion time. For chromium removal, three microemulsion extraction methods were evaluated: Method 1, in a Winsor II region, using as aqueous phase the acid digestion solution; Method 2, in a Winsor IV region, being obtained by the addition of the acid digestion solution to a microemulsion phase, whose aqueous phase is distilled water, until the formation of Winsor II system; and Method 3, in a Winsor III region, consisting in the formation of a Winsor III region using as aqueous phase the acid digestion solution, diluted in NaOH 0.01N. Seeking to optimize the extraction process only Method 1 (Systems I, II, and VIII) and Method 2 (System IX) were evaluated, being chosen points inside the interest regions (studied domains) to study the influence of contact time and pH in the extraction percentiles. The studied systems present the following compositions: System I: Surfactant Saponified coconut oil, Cosurfactant 1-Butanol, Oil phase Kerosene, Aqueous phase 2% NaCl solution; System II: Aqueous phase Acid digestion solution with pH adjusted using KOH (pH 3.5); System VIII: Aqueous phase - Acid digestion solution (pH 0.06); and System IX Aqueous phase Distilled water (pH 10.24), the other phases of Systems II, VIII and IX are similar to System I. Method 2 showed to be the more efficient one regarding chromium extraction percentile (up to 96.59% - pH 3.5). Considering that with Method 2 the microemulsion region only appears in the Winsor II region, it was studied Method 3 (System X) for the evaluation and characterization of a triphasic system, seeking to compare with a biphases system. System X is composed by: Surfactant Saponified coconut oil, Cosurfactant 1-Butanol, Oil phase Kerosene, Aqueous phase Acid digestion solution diluted with water and with its pH adjusted using 0.01N NaOH solution. The biphasic and triphasic microemulsion systems were analyzed regarding its viscosity, extraction efficiency and drop effective diameter. The experimental results showed that for viscosity studies the obtained values were low for all studied systems, the diameter of the drop is smaller in the Winsor II region, with 15.5 nm, reaching 46.0 nm in Winsor III region, being this difference attributed to variations in system compositions and micelle geometry. In chromium extraction, these points showed similar results, being achieved 99.76% for Winsor II system and 99.62% for Winsor III system. Winsor III system showed to be more efficient due to the obtaining of a icroemulsion with smaller volume, with the possibility to recover the oil phase in excess, and the use of a smaller proportion of surfactant and cosurfactant (C/S)

Extração e análise da fração lipídica da microalga monoraphidium sp., síntese e caracterização do seu biodiesel

The cultivation of microalgae biomass in order to produce biodiesel arises as an extremely promising aspect, in that the microalgae culture includes short cycle of reproduction, smaller areas for planting and residual biomass rich in protein content. The present dissertation evaluates the performance and features, through spectrometry in the region of infrared with transformed Fourier (FTIR) and spectrometry in the region of UVvisible (UV-Vis), of the extracted lipid material (LM) using different techniques of cell wall disruption (mechanical agitation at low and at high spin and agitation associated with cavitation). The technique of gas chromatography (GC) brought to light the success of alkaline transesterification in the conversion of oil into methyl monoesters (MME), which was also analyzed by spectroscopic techniques (FTIR, proton magnetic resonance (1H NMR) and carbon (13C NMR). Through thermogravimetric analysis (TGA) were analyzed the lipid material (LM), biodiesel and the microalgae biomass. The method which provided the best results concerning the efficiency in extraction of the LP of Monoraphidium sp. (12,51%) was by mechanical agitation at high spin (14 000 rpm), for 2 hours being the ideal time, as shown by the t test. The spectroscopic techniques (1H NMR, 13C NMR and FTIR) confirmed that the structure of methyl monoesters and the chromatographic data (CG) revealed a high content of saturated fatty acid esters (about 70%) being the major constituent eicosanoic acid (33,7%), which justifies the high thermal stability of microalgae biodiesel. The TGA also ratified the conversion rate (96%) of LM into MME, pointing out the quantitative results compatible with the values obtained through GC (about 98%) and confirmed the efficiency of the extraction methods used, showing that may be a good technique to confirm the extraction of these materials. The content of LM microalgae obtained (12,51%) indicates good potential for using such material as a raw material for biodiesel production, when compared to oil content which can be obtained from traditional oil for this use, since the productivity of microalgae per hectare is much larger and requires an extremely reduced period to renew its cultivation

Identificação e comparação entre controle preditivo com modelo não linear e PI sintonizados com PSO em sistema de separação gravitacional de águia-óleo

The separation methods are reduced applications as a result of the operational costs, the low output and the long time to separate the uids. But, these treatment methods are important because of the need for extraction of unwanted contaminants in the oil production. The water and the concentration of oil in water should be minimal (around 40 to 20 ppm) in order to take it to the sea. Because of the need of primary treatment, the objective of this project is to study and implement algorithms for identification of polynomial NARX (Nonlinear Auto-Regressive with Exogenous Input) models in closed loop, implement a structural identification, and compare strategies using PI control and updated on-line NARX predictive models on a combination of three-phase separator in series with three hydro cyclones batteries. The main goal of this project is to: obtain an optimized process of phase separation that will regulate the system, even in the presence of oil gushes; Show that it is possible to get optimized tunings for controllers analyzing the mesh as a whole, and evaluate and compare the strategies of PI and predictive control applied to the process. To accomplish these goals a simulator was used to represent the three phase separator and hydro cyclones. Algorithms were developed for system identification (NARX) using RLS(Recursive Least Square), along with methods for structure models detection. Predictive Control Algorithms were also implemented with NARX model updated on-line, and optimization algorithms using PSO (Particle Swarm Optimization). This project ends with a comparison of results obtained from the use of PI and predictive controllers (both with optimal state through the algorithm of cloud particles) in the simulated system. Thus, concluding that the performed optimizations make the system less sensitive to external perturbations and when optimized, the two controllers show similar results with the assessment of predictive control somewhat less sensitive to disturbances

Utilização de extrato de cogumelo como antioxidante natural em óleo vegetal

Conduziu-se este trabalho, com o objetivo de avaliar a atividade antioxidante de diferentes extratos de cogumelo Agaricus blazei, bem como a estabilidade oxidativa do óleo de soja adicionado de extrato de cogumelo. O cogumelo seco em estufa a 55ºC e triturado (10 g) fui submetido à extração, à temperatura ambiente, com 100 mL de metanol e metanol:água (1:1) com duração de 6 e 12 horas para ambas as extrações. O extrato de maior atividade antioxidante, conforme o método DPPH, foi aplicado em óleo de soja na concentração de 0,1% de compostos fenólicos totais e, então, submetido ao método do Rancimat e ao teste acelerado em estufa a 60ºC por um período de 16 dias. Amostras de óleo foram retiradas da estufa cada 4 dias e analisadas quanto ao índice de peróxidos e dienos conjugados. Como parâmetros de comparação, foram utilizados os antioxidantes sintéticos BHT (100 mg/kg), TBHQ (50 mg/kg) e o óleo de soja isento de antioxidantes (controle). Os resultados demonstraram que o extrato metanólico:aquoso, com 6 horas de extração, apresentou maior atividade antioxidante. A aplicação desse extrato em óleo de soja proporcionou a seguinte ordem em relação à estabilidade oxidativa: TBHQ > extrato de cogumelo > BHT = óleo de soja (controle). O extrato de cogumelo também foi eficiente em relação à formação de peróxidos e dienos conjugados que, apesar de aumentarem ao longo do tempo, foi menor que o BHT, porém maior que o TBHQ. O extrato de cogumelo apresentou-se efetivo na proteção do óleo, podendo ser considerado um potencial antioxidante natural.

Análise de extração de madeira de eucalipto com forwarder em floresta de primeira e segunda rotação

Pós-graduação em Agronomia (Energia na Agricultura) - FCA

Caracterização e estudo do comportamento térmico do óleo extraído da semente de mamão formosa (Carica papaya L.)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desenvolvimento de método analítico para determinação do teor de etanol em óleo lubrificante usado proveniente de motores ciclo Otto

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Épocas de plantio, idades e horários de colheita na produção e qualidade do óleo essencial de Lippia alba (Mill.) N.E. Br., quimiotipo limoneno-carvona

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)