Preparação de sílica organofuncionalizada à base de zircônia e estudos de adsorção de hidrocarbonetos policíclicos aromáticos e pesticidas organoclorados

O trabalho realizado conjuga informações de preparação e caracterização de materiais à base de sílica, com avaliação de possível aplicação potencial na área de química analítica ambiental. As sílicas organofuncionalizadas foram preparadas segundo 2 métodos: grafting e sol-gel. Os 4 sólidos obtidos por grafting diferem essencialmente na natureza da esfera de coordenação em torno do centro metálico (átomo de zircônio), enquanto que os 2 sólidos obtidos pelo processo sol-gel são sólidos híbridos, contendo ligantes indenil, grupos silanóis e etóxidos na superfície, diferindo entre si pela presença de centro metálico. Os teores de metal, determinados por RBS, nas sílicas organofuncionalizadas ficaram em torno de 0,3 % para os sólidos preparados por grafting e 4,5 %,no caso, do sólido preparado por sol-gel. A análise por DRIFTS confirmou a presença dos ligantes orgânicos e, ainda, grupos silanóis residuais nos adsorventes preparados por grafting. A capacidade de adsorção das sílicas organofuncionalizadas foi avaliada frente a duas famílias de compostos: HPAs e pesticidas organoclorados. A identificação e quantificação dos HPAs foi conduzida através de cromatografia gasosa com detector seletivo de massas. Os resultados da capacidade de adsorção para os 16 HPAs prioritários não foram quantitativamente considerados satisfatórios, em parte devido à dificuldade de solubilidade em água. A determinação quantitativa da eficiência dos adsorventes sólidos, na pré-concentração/extração dos pesticidas organoclorados, foi realizada através da cromatografia gasosa com detector de captura de elétrons. Os resultados de recuperação, para os compostos organoclorados: heptacloro epóxido, dieldrin e endrin foram considerados satisfatórios e em concordância com valores encontrados com o adsorvente comercial LC-18. O lindano apresentou boa recuperação especificadamente nos adsorventes preparados por sol-gel. De uma forma geral, os resultados indicam a possibilidade de utilização futura dos adsorventes sólidos preparados em protocolos de pré-concentração/extração de organoclorados a nível de traços.

Avaliação da contaminação de solos por hidrocarbonetos e metais pesados em diques de contenção

A meta dessa dissertação foi estudar a possibilidade de contaminação de um solo por hidrocarbonetos e metais pesados associados em zona industrial, estabelecendo uma metodologia de amostragem para avaliação de solos potencialmente contaminados. Para estudo de caso foi selecionada uma refinaria de petróleo localizada em território nacional. Conjuntamente com a metodologia de amostragem, foram estabelecidos como objetivos: a caracterização e avaliação do solo, a identificação dos possíveis “hot spot’s” para servir de subsídios para o monitoramento em investigações mais detalhadas do local e a avaliação da eficiência das barreiras argilosas que compõem os diques dos tanques. Foram investigados os solos que compõem os diques de contenção dos tanques armazenadores de petróleo. As diversas operações realizadas na área são fontes potencias de adição de contaminantes, que ocorrem, normalmente, em pequenas doses e de maneira contínua, pois a fonte nunca é estancada. Foram estabelecidas duas etapas de investigação: uma preliminar, que se consistiu em um levantamento do histórico da área, listando as evidências que pudessem indicar quais locais poderiam ser focos de contaminação A partir dos dados levantados na investigação preliminar foi feito o planejamento de uma campanha de amostragem para a coleta de amostras de solo. Além das análises usuais de caracterização, foram executadas análises de Hidrocarbonetos Totais de Petróleo (TPH Total Petroleum Hydrocarbon) e dos metais cádmio, chumbo, cromo, níquel e mercúrio. Para o enquadramento da área sob o ponto de vista de área contaminada foram utilizados como valores orientadores a “Nova Lista da Holanda” e os “Valores orientadores para solos e águas subterrâneas para o estado de São Paulo”. Dos quatro pontos amostrados, um foi classificado como um “hot spot”, atingindo valores que classificam a área como contaminada. Foi constatado que as barreiras argilosas que compõem os diques de contenção junto aos tanques de armazenamento são ineficientes, ou seja, os hidrocarbonetos estão percolando através dos diques de contenção.

Desenvolvimento e caracterização de revestimentos protetores contra carburização em tubos de pirólise de hidrocarbonetos na produção de olefinas

Este trabalho consistiu no desenvolvimento de revestimentos protetores contra carburização em ligas HP-40Nb, utilizadas na em fornos de pirólise para produção de olefinas, e do desenvolvimento de aparatos e técnicas para o teste, avaliação e caracterização destes revestimentos em ambientes fortemente carburizantes. Foram testados vários tipos de revestimentos, podendo estes ser resumidos em três grupos: i) camada de difusão de elementos específicos para o interior do metal (Al, Cu e Sn); ii) recobrimento com liga metálica (Ni-50Cr e Ni-5Al) e iii) recobrimento cerâmico (Al2O3, Cr2O3 e Al2O3 - TiO2). Além de revestimentos e camadas de difusão, um quarto tipo de material foi testado em sua resistência à carburização: ligas do tipo Fe-Cr- Al. A fim de testar os revestimentos e materiais desenvolvidos foram testados vários meios carburizantes. O que se mostrou mais adequado foi a mistura gasosa de hidrogênio e n-hexano, a uma temperatura de 1050°C. Foi construído um aparato exclusivamente para estes ensaios de carburização, o qual também foi utilizado para realizar os tratamentos de difusão necessários para produzir alguns dos revestimentos. A avaliação da resistência a carburização dos revestimentos e materiais foi feita por medição da profundidade de avanço da zona de precipitação de carbetos causada pela carburização, feito com auxílio de microscópio ótico. Os resultados dos ensaios mostraram que as camadas de difusão de alumínio, o revestimento da liga Ni-50Cr, o revestimento cerâmico de Al2O3 e as ligas Fe-Cr-Al tiveram bom ou ótimo desempenho como barreiras contra a carburização. Os outros revestimentos ou permitiram a penetração de carbono no metal base ou causaram uma deposição exagerada de coque na superfície dos corpos de prova.

Encapsulamento de solos contaminados por hidrocarbonetos

Este trabalho analisou a remediação de solos contaminados por hidrocarbonetos através do método de encapsulamento de contaminantes, o qual consiste na solidificação da camada e na estabilização química dos contaminantes por meio da adição de um agente cimentante, normalmente o cimento ou a cal. Este método proporciona a redução do potencial de toxicidade do contaminante, diminuindo e, em alguns casos, eliminando a presença do contaminante no lixiviado da camada tratada. São observadas outras vantagens do emprego do método de encapsulamento, dentre elas a elevada resistência da camada tratada devido à cimentação. Nesta pesquisa o método de encapsulamento de contaminantes foi analisado quanto ao seu emprego a contaminantes orgânicos, especificamente os hidrocarbonetos. Para tal, foi construído um equipamento de lixiviação em coluna de acordo com norma ASTM D 4874 para a análise do método para diferentes quantidades de contaminante presentes no solo, bem como para crescentes quantidades de agente cimentante. Da mesma forma, foram realizados ensaios de lixiviação pelo método proposto pela ABNT (NBR 10.005) para fins de comparação dos resultados. Os ensaios de lixiviação realizados no equipamento em coluna foram considerados mais consistentes devido a este possibilitar a simulação das condições de campo, tais como a influência do grau de compactação do material e variações da condutividade hidráulica do solo encapsulado. Constatou-se que a presença de cimento alterou apenas o volume de lixiviado, sem que mudanças na concentração do contaminante fossem observadas no fluido percolado Analisou-se a resistência à compressão não confinada em amostras de solos contaminados tratados pelo método proposto, onde se observou um acréscimo da resistência para crescentes quantidades de agente cimentante, bem como decréscimo da mesma para crescentes quantidades de contaminante adicionados ao solo. Em ambos os ensaios, concluiu-se que a quantidade de cimento e o grau de contaminação do solo são fatores determinantes na eficácia do tratamento.

Hidrocarbonetos policíclicos aromáticos em sedimentos de fundo do estuário do rio Potengi, região da grande Natal (RN): implicações ambientais

Estuaries are environments prone to the input of chemical pollutants of various kinds and origins, including polycyclic aromatic hydrocarbons (PAHs). Anthropogenic PAHs may have two possible sources: pyrolytic (with four or more aromatic rings and low degree of alkylation) and petrogenic (with two and three aromatic rings and high degree of alkylation). This study aimed to evaluate the levels, distribution and possible sources of polycyclic aromatic hydrocarbons in the estuary of the Potengi river, Natal, Brazil. Samples of bottom sediments were collected in the final 12 km of the estuary until its mouth to the sea, where the urbanization of the Great Natal is more concentrated. Sampling was performed on 12 cross sections, with three stations each, totaling 36 samples, identified as T1 to T36. The non alkylated and alkylated PAHs were analyzed by gas chromatography coupled to mass spectrometry (GC / MS). PAHs were detected in all 36 stations with total concentration on each varying 174-109407 ng g-1. These values are comparable to those of several estuarine regions worldwide with high anthropogenic influence, suggesting the record of diffuse contamination installed in the estuary. PAHs profiles were similar for most stations. In 32 of the 36 stations, low molecular weight PAHs (with 2 and 3 ring: naphthalene, phenanthrene and their alkylated homologues) prevailed, which ranged from 54% to 100% of the total PAH, indicating that leaks, spills and combustion fuels are the dominant source of PAH pollution in the estuary. The level of contamination by PAHs in most stations suggests that there is potential risk of occasional adverse biological effects, but in some stations adverse impacts on the biota may occur frequently. The diagnostic ratios could differentiate sources of PAHs in sediments of the estuary, which were divided into three groups: petrogenic, pyrolytic and mixing of sources. The urban concentration of the Great Natal and the various industrial activities associated with it can be blamed as potential sources of PAHs in bottom sediments of the estuary studied. The data presented highlight the need to control the causes of existing pollution in the estuary

Gerenciamento de alarmes em plataformas marítimas de produção de hidrocarbonetos: metodologia e estudo de caso

In the operational context of industrial processes, alarm, by definition, is a warning to the operator that an action with limited time to run is required, while the event is a change of state information, which does not require action by the operator, therefore should not be advertised, and only stored for analysis of maintenance, incidents and used for signaling / monitoring (EEMUA, 2007). However, alarms and events are often confused and improperly configured similarly by developers of automation systems. This practice results in a high amount of pseudo-alarms during the operation of industrial processes. The high number of alarms is a major obstacle to improving operational efficiency, making it difficult to identify problems and increasing the time to respond to abnormalities. The main consequences of this scenario are the increased risk to personal safety, facilities, environment deterioration and loss of production. The aim of this paper is to present a philosophy for setting up a system of supervision and control, developed with the aim of reducing the amount of pseudo-alarms and increase reliability of the information that the system provides. A real case study was conducted in the automation system of the offshore production of hydrocarbons from Petrobras in Rio Grande do Norte, in order to validate the application of this new methodology. The work followed the premises of the tool presented in ISA SP18.2. 2009, called "life cycle alarm . After the implementation of methodology there was a significant reduction in the number of alarms

Hidrocarbonetos alifáticos em sedimentos de fundo do estuário do Rio Potengi, grande Natal (RN): implicações ambientais

The Potengi river estuary is located in the region of Natal (RN, Brazil), comprising a population of approximately 1,000,000 inhabitants. Besides the dominant urban presence, the estuary has fragments of mangrove forest. The objective of this study is to determine the aliphatic hydrocarbons found in the bottom sediments of this estuary, identifying their levels, distribution and their possible origins through the diagnostic rates, indexes and results comparisons with the local anthropic and natural characteristics. The samples were obtained according to a plan that allowed sampling of the estuary up to 12 km upstream from it as mounth. 36 stations were selected, grouped into 12 cross sections through the course of the river and spaced on average by 1 km. Each section consisted of three stations: the right margin, the deepest point and the left margin. The hydrocarbon n-alkanes from C10 to C36, the isoprenoids pristane and phytane, the unresolved complex mixture (UCM) and the total resolved hydrocarbons were analyzed by gas chromatography. N-alkanes, pristane, phytane and UCM were detected only at some stations. In the other, the concentration was below the detection limit defined by the analytical method (0.1 mg / kg), preventing them from being analyzed to determine the origin of the material found. By using different parameters, the results show that the estuary receives both the input of petrogenic hydrocarbons, but also of biogenic hydrocarbons, featuring a mixture of sources and relatively impacted portions. Based on the characteristics and activities found in the region, it is possible to affirm that petrogenic sources related to oil products enter the estuary via urban runoff or boats traffic, boat washing and fueling. Turning to the biogenic source, the predominant origin was terrestrial, characterized by vascular plants, indicating contribution of mangrove vegetation. It was evident the presence of, at specific points in the estuary, hydrocarbon pollution, and, therefore is recommended the adoption of actions aimed at interrupting or, at least, mitigating the sources potentially capable of damp petrogenic hydrocarbons in the estuary studied.

Biodegradação de hidrocarbonetos aromáticos policíclicos: prospecção metagenômica e modelagem computacional 3-D de proteínas

Knowledge of the native prokaryotes in hazardous locations favors the application of biotechnology for bioremediation. Independent strategies for cultivation and metagenomics contribute to further microbiological knowledge, enabling studies with non-cultivable about the "native microbiological status and its potential role in bioremediation, for example, of polycyclic aromatic hydrocarbons (HPA's). Considering the biome mangrove interface fragile and critical bordering the ocean, this study characterizes the native microbiota mangrove potential biodegradability of HPA's using a biomarker for molecular detection and assessment of bacterial diversity by PCR in areas under the influence of oil companies in the Basin Petroleum Geology Potiguar (BPP). We chose PcaF, a metabolic enzyme, to be the molecular biomarker in a PCR-DGGE detection of prokaryotes that degrade HPA s. The PCR-DGGE fingerprints obtained from Paracuru-CE, Fortim-CE and Areia Branca-RN samples revealed the occurrence of fluctuations of microbial communities according to the sampling periods and in response to the impact of oil. In the analysis of microbial communities interference of the oil industry, in Areia Branca-RN and Paracuru-CE was observed that oil is a determinant of microbial diversity. Fortim-CE probably has no direct influence with the oil activity. In order to obtain data for better understanding the transport and biodegradation of HPA's, there were conducted in silico studies with modeling and simulation from obtaining 3-D models of proteins involved in the degradation of phenanthrene in the transport of HPA's and also getting the 3-D model of the enzyme PcaF used as molecular marker in this study. Were realized docking studies with substrates and products to a better understanding about the transport mechanism and catalysis of HPA s

Metagenômica: busca de novos genes envolvidos com a biodegradação de hidrocarbonetos

Industrial activities, oil spills and its derivatives, as well as the incomplete combustion of fossil fuels have caused a great accumulation of hydrocarbons in the environment. The number of microorganisms on the planet is estimated at 1030 and prokaryotes the most abundant. They colonized diverse environments for thousands of years, including those considered extreme and represent an untapped source of metabolic and genetic diversity with a large biotechnological potential. It is also known that certain microorganisms have the enzymatic capacity to degrade petroleum hydrocarbons and, in many ecosystems, there is an indigenous community capable of performing this function. The metagenomic has revolutionized the microbiology allowing access uncultured microbial communities, being a powerful tool for elucidation of their ecological functions and metabolic profiles, as well as for identification of new biomolecules. Thus, this study applied metagenomic approaches not only for functional selection of genes involved in biodegradation and emulsification processes of the petroleum-derived hydrocarbons, but also to describe the taxonomic and metabolic composition of two metagenomes from aquatic microbiome. We analyzed 123.116 (365 ± 118 bp) and 127.563 sequences (352 ± 120 bp) of marine and estuarine metagenomes, respectively. Eight clones were found, four involved in the petroleum biodegradation and four were able to emulsify kerosene indicating their abilities in biosurfactants synthesis. Therefore, the metagenomic analyses performed were efficient not only in the search of bioproducts of biotechnological interest and in the analysis of the functional and taxonomic profile of the metagenomes studied as well

Análise de desempenho de um refrigerador de pequeno porte com drop in de refrigerantes hidrocarbonetos

From what was stated in the Montreal Protocol, the researchers and refrigeration industry seek substitutes for synthetic refrigerants -chlorofluorocarbons (CFCs) and HCFCs (HCFC) - that contribute to the depletion of the ozone layer. The phase-out of these substances was started using as one of the replacement alternatives the synthetic fluids based on hydro fluorocarbons (HFCs) that have zero potential depletion of the ozone layer. However, contribute to the process of global warming. HFC refrigerants are greenhouse gases and are part of the group of gases whose emissions must be reduced as the Kyoto Protocol says. The hydrocarbons (HC's), for not contribute to the depletion of the ozone layer, because they have very low global warming potential, and are found abundantly in nature, has been presented as an alternative, and therefore, are being used in new home refrigeration equipment in several countries. In Brazil, due to incipient production of domestic refrigerators using HC's, the transition refrigerants remain on the scene for some years. This dissertation deals with an experimental evaluation of the conduct of a drinking fountain designed to work with HFC (R-134a), operating with a mixture of HC's or isobutane (R-600a) without any modification to the system or the lubricating oil. In the refrigeration laboratory of Federal University of Rio Grande do Norte were installed, in a drinking fountain, temperature and pressure sensors at strategic points in the refrigeration cycle, connected to an acquisition system of computerized data, to enable the mapping and thermodynamics analysis of the device operating with R-134a or with a mixture of HC's or with R-600a. The refrigerator-test operating with the natural fluids (mixture of HC's or R-600a) had a coefficient of performance (COP) lower than the R-134a

Remoção de hidrocarbonetos do gás natural visando o ajuste do índice de metano

The use of the natural gas is growing year after year in the whole world and also in Brazil. It is verified that in the last five years the profile of natural gas consumption reached a great advance and investments had been carried through in this area. In the oil industry, the use of the natural gas for fuel in the drive of engines is usual for a long date. It is also used to put into motion equipment, or still, to generate electric power. Such engines are based on the motor cycle of combustion Otto, who requires a natural gas with well definite specification, conferring characteristic anti-detonating necessary to the equipment performance for projects based on this cycle. In this work, process routes and thermodynamic conditions had been selected and evaluated. Based on simulation assays carried out in commercial simulators the content of the methane index of the effluent gas were evaluated at various ranges of pressure, temperature, flowrate, molecular weight and chemical nature and composition of the absorbent. As final result, it was established a route based on process efficiency, optimized consumption of energy and absorbent. Thereby, it serves as base for the compact equipment conception to be used in locu into the industry for the removal of hydrocarbon from the natural gas produced

Degradação fotoquímica de hidrocarbonetos da gasolina em efluentes aquosos

Photo-oxidation processes of toxic organic compounds have been widely studied. This work seeks the application of the photo-Fenton process for the degradation of hydrocarbons in water. The gasoline found in the refinery, without additives and alcohol, was used as the model pollutant. The effects of the concentration of the following substances have been properly evaluated: hydrogen peroxide (100-200 mM), iron ions (0.5-1 mM) and sodium chloride (200 2000 ppm). The experiments were accomplished in reactor with UV lamp and in a falling film solar reactor. The photo-oxidation process was monitored by measurements of the absorption spectra, total organic carbon (TOC) and chemical oxygen demand (COD). Experimental results demonstrated that the photo-Fenton process is feasible for the treatment of wastewaters containing aliphatic hydrocarbons, inclusive in the presence of salts. These conditions are similar to the water produced by the petroleum fields, generated in the extraction and production of petroleum. A neural network model of process correlated well the observed data for the photooxidation process of hydrocarbons