Remediação de solos contaminados com diesel por lavagem com solução de tensoativos

Combating pollution of soils is a challenge that has concerned researchers from different areas and motivated the search for technologies that aim the recovery of degraded soils. Literature shows numerous processes that have been proposed with the intent of remediating soils contaminated by oils and other by-products of the oil industry, considering that the processes available have, generally, high operating costs, this work proposes a costeffective alternative to the treatment of Diesel-contaminated soils. The washing solutions were prepared using water as aqueous phase, the saponified coconut oil (OCS) as surfactant and n-butanol as co-surfactant. In this study, the soil was characterized by physical and chemical analyses. The study of diesel desorption from the soil was held in bath, using hexane and washing solutions, which had 10 and 20 wt.% active matter (AM - co-surfactant/surfactants) respectively. The study of the influence of active matter concentration and temperature in bath agitated used an experimental planning. The experiment also developed a system of percolation in bed to wash the soil and studied the influence of the concentration of active substance and volume of washing solution using an experimental planning. The optimal times to achieve hexane extraction were 30 and 180 min, while the best results using a 10% AM was 60 min and using a 20% AM was 120 min. The results of the experimental planning on bath showed that the maximum diesel removal was obtained when at a 20 wt.% of AM and under 50 °C, removing 99.92% of the oil. As for experiments in the system of percolation soil bed, the maximum diesel removal was high when the volume of the washing solution was of 5 L and the concentration of 20% AM. This experiment concluded that the concentration of AM and the temperature were vital to bath experiments for diesel removal, while in the system of percolation soil bed only concentration of AM influenced the soil remediation

Novas formulações de fluidos de corte: otimização, propriedades e recuperação do óleo usado

Cutting fluids are lubricants used in metal-mechanical industries. Their complex composition varies according to the type of operation carried out, also depending on the metals under treatment or investigation. Due to the high amount of mineral oil produced in Northeastern Brazil, we have detected the need to better use this class of material. In this work, two novel formulations have been tested, both based on naphthenic mineral oil and additives, such as: an emulsifying agent (A), an anticorrosion agent (B), a biocide (C) and an antifoam agent (D). Each formulation was prepared by mixing the additives in the mineral oil at a 700-rpm stirring velocity for 10 min, at 25°C, employing a 24 factorial planning. The formulations were characterized by means of density, total acid number (TAN), viscosity, flash point and anticorrosion activity. In a subsequent study, oil-in-water emulsions were prepared from these novel formulations. The emulsions were analyzed in terms of stability, corrosion degree, percentage of foam formation, conductivity, accelerated stability and particle size. The samples were appropriately labeled, and, in special, two of them were selected for featuring emulsion properties which were closer to those of the standards chosen as references (commercial cutting oils). Investigations were undertaken on the ability of NaCl and CaCl2 to destabilize the emulsions, at concentrations of 2%, 5% and 10%, at an 800-rpm stirring velocity for 5 min and temperatures of 25º, 40º, 50º and 60ºC. The recovered oils were chemically altered by reincorporating the same additives used in the original formulations, followed by preparation of emulsions with the same concentrations as those of the initial ones. The purpose was to assess the possibility of reusing the recovered oil. The effluents generated during the emulsion destabilization step were characterized via turbidity index, contents of oil and grease, pH, and contents of anions and cations, observing compliance with the parameters established by the current environmental legislation (Brazil s CONAMA 357/05 resolution). It could be concluded that the formulations presented excellent physicochemical properties as compared to commercial cutting fluids, showing that the quality of the newly-prepared fluids is superior to that of the formulations available in the market, enabling technically and environmentally-safe applications

Remoção, por flotação, de óleo em águas produzidas na indústria de petróleo: eficiência e modelagem do processo

The separation oil-water by the use of flotation process is characterized by the involvement between the liquid and gas phases. For the comprehension of this process, it s necessary to analyze the physical and chemical properties command float flotation, defining the nature and forces over the particles. The interface chemistry has an important role on the flotation technology once, by dispersion of a gas phase into a liquid mixture the particles desired get stuck into air bubbles, being conduced to a superficial layer where can be physically separated. Through the study of interface interaction involved in the system used for this work, was possible to apply the results in an mathematical model able to determine the probability of flotation using a different view related to petroleum emulsions such as oil-water. The terms of probability of flotation correlate the collision and addition between particles of oil and air bubbles, that as more collisions, better is the probability of flotation. The additional probability was analyzed by the isotherm of absorption from Freundlich, represents itself the add probability between air bubbles and oil particles. The mathematical scheme for float flotation involved the injected air flow, the size of bubbles and quantity for second, the volume of float cell, viscosity of environment and concentration of demulsifier. The results shown that the float agent developed by castor oil, pos pH variation, salt quantity, temperature, concentration and water-oil quantity, presented efficient extraction of oil from water, up to 95%, using concentrations around 11 ppm of demulsifier. The best results were compared to other commercial products, codified by ―W‖ and ―Z‖, being observed an equivalent demulsifier power between Agflot and commercial product ―W‖ and superior to commercial product ―Z‖

Utilização de uma coluna de flotação para remoção de compostos orgânicos da água de produção

Innovative technologies using surfactant materials have applicability in several industrial fields, including petroleum and gas areas. This study seeks to investigate the use of a surfactant derived from coconut oil (SCO saponified coconut oil) in the recovery process of organic compounds that are present in oily effluents from petroleum industry. For this end, experiments were accomplished in a column of small dimension objectifying to verify the influence of the surfactant SCO in the efficiency of oil removal. This way, they were prepared emulsions with amount it fastens of oil (50, 100, 200 and 400 ppm), being determined the great concentrations of surfactant for each one of them. Some rehearsals were still accomplished with produced water of the industry of the petroleum to compare the result with the one of the emulsions. According to the experiments, it was verified that an increase of the surfactant concentration does not implicate in a greater oil removal. The separation process use gaseous bubbles formed when a gas stream pass a liquid column, when low surfactant concentrations are used, it occurs the coalescence of the dispersed oil droplets and their transport to the top of the column, forming a new continuous phase. Such surfactants lead to a gas-liquid interface saturation, depending on the used surfactant concentration, affecting the flotation process and influencing in the removal capacity of the oily dispersed phase. A porous plate filter, with pore size varying from 40 to 250 mm, was placed at the base of the column to allow a hydrodynamic stable operation. During the experimental procedures, the operating volume of phase liquid was held constant and the rate of air flow varied in each experiment. The resulting experimental of the study hydrodynamic demonstrated what the capturing of the oil was influenced by diameter of the bubbles and air flow. With the increase flow of 300 about to 900 cm3.min-1, occurred an increase in the removal of oil phase of 44% about to 66% and the removal kinetic of oil was defined as a reaction of 1° order.

Tratamento de borra de petróleo com sistemas microemulsionados

During the storage of oil, sludge is formed in the bottoms of tanks, due to decantation, since the sludge is composed of a large quantity of oil (heavy petroleum fractions), water and solids. The oil sludge is a complex viscous mixture which is considered as a hazardous waste. It is then necessary to develop methods and technologies that optimize the cleaning process, oil extraction and applications in industry. Therefore, this study aimed to determine the composition of the oil sludge, to obtain and characterize microemulsion systems (MES), and to study their applications in the treatment of sludge. In this context, the Soxhlet extraction of crude oil sludge and aged sludge was carried out, and allowing to quantify the oil (43.9 % and 84.7 % - 13 ºAPI), water (38.7 % and 9.15 %) and solid (17.3 % and 6.15 %) contents, respectively. The residues were characterized using the techniques of X-ray fluorescence (XRF), Xray diffraction (XRD) and transmission Infrared (FT-IR). The XRF technique determined the presence of iron and sulfur in higher proportions, confirming by XRD the presence of the following minerals: Pyrite (FeS2), Pyrrhotite (FeS) and Magnetite (Fe3O4). The FT-IR showed the presence of heavy oil fractions. In parallel, twelve MES were prepared, combining the following constituents: two nonionic surfactants (Unitol L90 and Renex 110 - S), three cosurfactants (butanol, sec-butanol and isoamyl alcohol - C), three aqueous phase (tap water - ADT, acidic solution 6 % HCl, and saline solution - 3.5 % NaCl - AP) and an oil phase (kerosene - OP). From the obtained systems, a common point was chosen belonging to the microemulsion region (25 % [C+S] 5 % OP and AP 70 %), which was characterized at room temperature (25°C) by viscosity (Haake Rheometer Mars), particle diameter (Zeta Plus) and thermal stability. Mixtures with this composition were applied to oil sludge solubilization under agitation at a ratio of 1:4, by varying time and temperature. The efficiencies of solubilization were obtained excluding the solids, which ranged between 73.5 % and 95 %. Thus, two particular systems were selected for use in storage tanks, with efficiencies of oil sludge solubilization over 90 %, which proved the effectiveness of the MES. The factorial design delimited within the domain showed how the MES constituents affect the solubilization of aged oil sludge, as predictive models. The MES A was chosen as the best system, which solubilized a high amount of aged crude oil sludge (~ 151.7 g / L per MES)

Adubação química e orgânica na recuperação da fertilidade de subsolo degradado e na micorrização do Stryphnodendron polyphyllum

Com a construção da usina hidrelétrica de Ilha Solteira no final da década de 1960, algumas áreas foram desmatadas, servindo como área de empréstimo. Os solos dessas áreas foram retirados e estas adquiriram características físicas, químicas e biológicas distantes das ideais. Este trabalho objetivou avaliar os efeitos da aplicação da adubação química e orgânica na fertilidade do subsolo degradado e micorrização de Stryphnodendron polyphyllum (barbatimão). A área localiza-se na fazenda de Ensino, Pesquisa e Extensão (FEPE) da UNESP/Ilha Solteira, em Selvíria - MS. Com delineamento de blocos ao acaso, em parcelas de 250 m² (10 x 25 m), foram avaliados 10 tratamentos: testemunha; calagem; adubação N + P; calagem + N + P; N + P + aguapé; N + P + bagaço de cana; N + P + aguapé + bagaço de cana; calagem + N + P + aguapé; calagem + N + P + bagaço de cana; e calagem + N + P + bagaço de cana + aguapé. Avaliaram-se as características químicas do solo e o crescimento do barbatimão em cinco períodos (junho, agosto, novembro e dezembro de 2005 e março de 2006), e a micorrização, em março de 2006. Observou-se que o subsolo continuou apresentando caráter ácido e pobreza em nutrientes após um ano de avaliação. O crescimento da planta aumentou ao longo do período, com os maiores valores para os tratamentos que receberam calagem, adubação e resíduos orgânicos, especialmente o aguapé. A colonização micorrízica foi influenciada positivamente pela presença de resíduos orgânicos, e o número de esporos, pelos tratamentos com presença de aguapé.

Desenvolvimento e teste de um modelo estatístico de identificação das proporções de água produzida em zonas de produção de um campo maduro de petróleo

This study investigates the chemical species produced water from the reservoir areas of oil production in the field of Monte Alegre (onshore production) with a proposal of developing a model applied to the identification of the water produced in different zones or groups of zones.Starting from the concentrations of anions and cátions from water produced as input parameters in Linear Discriminate Analysis, it was possible to estimate and compare the model predictions respecting the particularities of their methods in order to ascertain which one would be most appropriate. The methods Resubstitution, Holdout Method and Lachenbruch were used for adjustment and general evaluation of the built models. Of the estimated models for Wells producing water for a single production area, the most suitable method was the "Holdout Method and had a hit rate of 90%. Discriminant functions (CV1, CV2 and CV3) estimated in this model were used to modeling new functions for samples ofartificial mixtures of produced water (producedin our laboratory) and samples of mixtures actualproduced water (water collected inwellsproducingmore thanonezone).The experiment with these mixtures was carried out according to a schedule experimental mixtures simplex type-centroid also was simulated in which the presence of water from steam injectionin these tanks fora part of amostras. Using graphs of two and three dimensions was possible to estimate the proportion of water in the production area

Recuperação do subsolo em área de empréstimo usada para construção de hidrelétrica

Áreas degradadas referem-se a ecossistemas alterados, onde perdas ou adições são as formas mais comuns de perturbações e degradações ambientais. As áreas de empréstimo em hidrelétricas podem ser consideradas áreas degradadas, pois delas foram retirados os horizontes superficiais do solo. Portanto, este trabalho teve como objetivo estudar a recuperação de atributos físicos e da matéria orgânica do subsolo de um Latossolo Vermelho distrófico, degradado pela retirada de solo para construção de usina hidrelétrica, por meio de adubação verde e aplicação de calcário e gesso. A pesquisa foi implantada em 1992 e os tratamentos constituíram-se de: testemunha (solo mobilizado e vegetação espontânea); mucuna-preta; guandu até 1994, seguido por feijão-de-porco; calcário + mucuna-preta; calcário + guandu até 1994, seguido por feijão-de-porco; calcário + gesso + mucuna-preta e calcário + gesso + guandu até 1994, seguido por feijão-de-porco. Os tratamentos foram implantados seguindo o esquema em blocos casualizados com quatro repetições. Após sete anos, em 1999, foram avaliadas a porosidade do solo, a macroporosidade, a microporosidade, a densidade do solo, matéria orgânica e a produção de massa seca da braquiária. Os tratamentos adotados estão contribuindo para a recuperação dos atributos físicos do subsolo exposto, e o tratamento com mucuna-preta, sem a correção do solo, tem se mostrado mais promissor. Os efeitos da recuperação do solo estão atingindo a profundidade de 0,00-0,10 m.

Recuperação de um solo degradado com a aplicação de adubos verdes e lodo de esgoto

A utilização incorreta dos solos vem causando alterações neles, tornando-os cada vez menos produtivos, aumentando as áreas com solos degradados. O presente trabalho teve por objetivos estudar ações para acelerar a formação do horizonte A de um Latossolo Vermelho degradado, via uso de adubos verdes, lodo de esgoto e cultivo de uma espécie arbórea nativa de Cerrado, e selecionar indicadores para detectar alterações da camada superficial do solo. O monitoramento das alterações do solo foi realizado anualmente. O delineamento experimental foi o de blocos casualizados com seis tratamentos, em cinco repetições. Os tratamentos foram: testemunha - solo exposto (sem manejo); vegetação nativa (Cerrado); espécie arbórea Astronium fraxinifolium; Astronium fraxinifolium + Canavalia ensiformis; Astronium fraxinifolium + Raphanus sativus; e Astronium fraxinifolium + Brachiaria decumbens + lodo de esgoto (60 t ha-1). Avaliou-se no solo: porosidade, densidade do solo, cátions trocáveis, pH, acidez potencial (H + Al), soma de bases (SB), saturação por bases (V), CTC e macrorganismos. Nos adubos verdes, foi avaliada a massa seca e, para a espécie arbórea, a altura e o diâmetro de caule. A mobilização do solo e a mobilização mais a adubação verde e o lodo de esgoto estão recuperando as propriedades do solo degradado, com comportamento semelhante entre elas após um ano de adoção. O melhor indicador físico das alterações do solo foi sua densidade. Os tratamentos adotados são semelhantes quanto à população de macrorganismos do solo e contribuindo positivamente para recuperação da macrofauna. A presença de larva e besouro foi indicadora da melhoria da macrofauna do solo.

Recuperação de área degradada por construção de hidroelétrica com adubação verde e corretivo

As áreas de empréstimo em hidrelétricas são as áreas remanescentes da construção da fundação da barragem e podem ser consideradas áreas degradadas, pois delas foram retirados os horizontes superficiais do solo. Este trabalho teve como objetivo estudar a recuperação de um Latossolo Vermelho distrófico, degradado por construção civil (Usina Hidrelétrica de Ilha Solteira-SP), por meio de adubação verde e aplicação de calagem e gessagem. Os tratamentos constituíram-se de: testemunha (solo mobilizado e vegetação espontânea); mucuna-preta e guandu até 1994. Depois foram substituídos por feijão-de-porco; calcário + mucuna-preta; calcário + guandu até 1994. Nova substituição foi feita por feijão-de-porco; calcário + gesso + mucuna-preta e calcário + gesso + guandu até 1994. Outra substituição foi feita por feijão-de-porco. Esses tratamentos foram estabelecidos em blocos casualizados com quatro repetições: após quatro anos com os adubos verdes, um ano com milho, um ano com aveia-preta e dois anos com braquiária. Foram avaliados: pH, teores de Ca2+, Mg2+, P, K, capacidade de troca catiônica, saturação por bases e teor de matéria orgânica. Os tratamentos adotados estão recuperando os atributos químicos do solo degradado, e a mucuna-preta apresentou os melhores resultados, quando comparada ao guandu e feijão-de-porco. Os efeitos da recuperação dos atributos químicos do solo alcançaram a profundidade de 0,0-0,2 m. As técnicas adotadas para recuperação desses atributos químicos (adubação verde, calagem e gessagem) no primeiro ano atingiram a profundidade do solo de 0,0-0,1 m e, somente após cinco anos, de 0,0-0,2 m.

Estabilidade de agregados de um latossolo vermelho degradado em recuperação com adubos verdes, calcário e gesso

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

Densidade do solo e infiltração de água como indicadores da qualidade física de um Latossolo Vermelho distrófico em recuperação

A necessidade cada vez maior de alimentos, espaço e condições para sobrevivência faz com que as interferências antrópicas no ambiente sejam cada vez maiores. Solos intensivamente cultivados e de forma inadequada são degradados, assim como a construção de obras civis no meio rural sem atender à legislação pertinente tudo isso tem ocasionado problemas ao meio. Várias técnicas têm sido utilizadas para recuperar esses solos, sendo a principal delas a adição de MO. Contudo, informações sobre tempo para recuperação do solo, influência dos tipos de material orgânico e indicadores das alterações ainda são escassas. Este trabalho objetivou avaliar a recuperação das propriedades de um Latossolo Vermelho distrófico, de onde foi retirado material usado na terraplanagem e nas fundações da usina hidrelétrica de Ilha Solteira-SP, utilizando-se como indicadores de qualidade física a densidade do solo e a taxa de infiltração de água. A pesquisa foi feita em uma área onde se retirou uma camada de solo de 8,60 m. O delineamento experimental foi em blocos casualizados, com cinco repetições e cinco tratamentos: testemunha (solo exposto sem técnicas de recuperação); espécie arbórea gonçalo-alves (Astronium fraxinifolium Schott); gonçalo-alves + feijão-de-porco (Canavalia ensiformis); gonçalo-alves + nabo forrageiro (Raphanus sativus); e gonçalo-alves + gramínea (Brachiaria decumbens) + lodo de esgoto (60 Mg ha-1). A densidade do solo foi avaliada antes e 356 dias após a implantação dos tratamentos, e a infiltração de água no solo foi determinada 188 dias depois da instalação dos tratamentos. Concluiu-se que ocorrem melhorias na qualidade do solo quando efetuado o seu preparo e a adição de lodo de esgoto e adubos verdes. A densidade do solo e a infiltração de água do solo são bons indicadores na avaliação dessas melhorias. As diferentes fontes de MO adicionadas ao solo e a ação do preparo deste interagem de maneira semelhante na recuperação da sua qualidade, porém a combinação lodo de esgoto mais braquiária proporciona maior altura de planta da espécie gonçalo-alves.

Período de recuperação do investimento em bomba hidráulica de melhor rendimento em sistemas de bombeamento na tarifa horossazonal verde

Neste trabalho, ajustou-se um modelo matemático para quantificar o efeito da variação do rendimento da bomba hidráulica na variação dos custos de um sistema de bombeamento, na estrutura tarifária horossazonal verde (subgrupo A4) e o tempo de recuperação do capital investido no equipamento de maior rendimento. em seguida, o mesmo foi aplicado a um sistema de bombeamento para suprimento de um sistema de irrigação do tipo pivô central. As opções de rendimento da bomba hidráulica foram: 69,5% (bomba 1), 73% (bomba 2) e 78% (bomba 3), cujos custos de aquisição foram, respectivamente, R$ 6.176,00, R$ 8.479,00 e R$ 15.509,00. Os resultados da aplicação do modelo mostraram que: i) a substituição da bomba 1 pela bomba 2 foi viável, sendo o período de recuperação de capital 3,4 anos; ii) a substituição da bomba 1 pela bomba 3 foi viável, sendo o período de recuperação de capital 9,2 anos; iii) a substituição da bomba 2 pela bomba 3 foi inviável, sendo o período de recuperação de capital 21,1 anos superior ao período de amortização do investimento na avaliação econômica, considerado 15 anos.

Estudo cinético da degradação térmica e catalítica de petróleo pesado usando Al-MCM-41

The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API º equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ° C and heating ratios (β) ranging from 5, 10 and 20 °C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41

Degradação térmica e catalítica do resíduo atmosférico de petróleo (RAT), utilizando materiais nanoestruturados do tipo SBA-15

In this work were synthesized and characterized the materials mesoporous SBA-15 and Al- SBA-15, Si / Al = 25, 50 and 75, discovered by researchers at the University of California- Santa Barbara, USA, with pore diameters ranging from 2 to 30 nm and wall thickness from 3.1 to 6.4 nm, making these promising materials in the field of catalysis, particularly for petroleum refining (catalytic cracking), as their mesopores facilitate access of the molecules constituting the oil to active sites, thereby increasing the production of hydrocarbons in the range of light and medium. To verify that the materials used as catalysts were successfully synthesized, they were characterized using techniques of X-ray diffraction (XRD), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). Aiming to check the catalytic activity thereof, a sample of atmospheric residue oil (ATR) from the pole Guamaré-RN was performed the process by means of thermogravimetry and thermal degradation of catalytic residue. Upon the curves, it was observed a reduction in the onset temperature of the decomposition process of catalytic ATR. For the kinetic model proposed by Flynn-Wall yielded some parameters to determine the apparent activation energy of decomposition, being shown the efficiency of mesoporous materials, since there was a decrease in the activation energy for the reactions using catalysts. The ATR was also subjected to pyrolysis process using a pyrolyzer with gas chromatography coupled to a mass spectrometer. Through the chromatograms obtained, there was an increase in the yield of the compounds in the range of gasoline and diesel from the catalytic pyrolysis, with emphasis on Al-SBA-15 (Si / Al = 25), which showed a percentage higher than the other catalysts. These results are due to the fact that the synthesized materials exhibit specific properties for application in the process of pyrolysis of complex molecules and high molecular weight as constituents of the ATR