Caracterização de água produzida na indústria de petróleo para fins de descarte e otimização do processo de separação óleo/água

The oil industry has several segments that can impact the environment. Among these, produced water which has been highlight in the environmental problem because of the great volume generated and its toxic composition. Those waters are the major source of waste in the oil industry. The composition of the produced water is strongly dependent on the production field. A good example is the wastewater produced on a Petrobras operating unit of Rio Grande do Norte and Ceará (UO-RNCE). A single effluent treatment station (ETS) of this unit receives effluent from 48 wells (onshore and offshore), which leads a large fluctuations in the water quality that can become a complicating factor for future treatment processes. The present work aims to realize a diagnosis of a sample of produced water from the OU - RNCE in compliance to certain physical and physico-chemical parameters (chloride concentration, conductivity, dissolved oxygen, pH, TOG (oil & grease), nitrate concentration, turbidity, salinity and temperature). The analysis of the effluent is accomplished by means of a MP TROLL 9500 Multiparameter probe, a TOG/TPH Infracal from Wilks Enterprise Corp. - Model HATR - T (TOG) and a MD-31 condutivimeter of Digimed. Results were analyzed by univariated and multivariated analysis (principal component analysis) associated statistical control charts. The multivariate analysis showed a negative correlation between dissolved oxygen and turbidity (-0.55) and positive correlations between salinity and chloride (1), conductivity, chloride and salinity (0.70). Multivariated analysis showed there are seven principal components which can explain the variability of the parameters. The variables, salinity, conductivity and chloride were the most important variables, with, higher sampling variance. Statistical control charts have helped to establish a general trend between the physical and chemical evaluated parameters

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

Otimização do processo de flotação de emulsão óleo/água através do planejamento fatorial completo

In recent decades, the generation of solid and liquid waste has increased substantially due to increased industrial activity that is directly linked to economic growth. For that is the most efficient process, it is inevitable generation of such wastes. In the oil industry, a major waste generated in oil exploration is produced water, which due to its complex composition and the large amount generated, has become a challenge, given the restrictions imposed by environmental laws regarding their disposal, making if necessary create alternatives for reuse or treatment in order to reduce the content of contaminants and reduce the harmful effects to the environment. This water can be present in free form or emulsified with the oil, when in the form of an emulsion of oil-water type, it is necessary to use chemicals to promote the separation and flotation is the treatment method which has proved to be more efficient, for it can remove much of the emulsified oil when compared to other methods. In this context, the object of this work was to study the individual effects and interactions of some physicochemical parameters of operations, based on previous work to a flotation cell used in the separation of synthetic emulsion oil / water in order to optimize the efficiency of the separation process through of the 24 full factorial design with center point. The response variables to evaluate the separation efficiency was the percentage of color and turbidity removal. The independent variables were: concentration of de-emulsifying, oil content in water, salinity and pH, these being fixed, minimum and maximum limits. The analysis of variance for the equation of the empirical model, was statistically significant and useful for predictive purposes the separation efficiency of the floater with R2 > 90%. The results showed that the oil content in water and the interaction between the oil content in water and salinity, showed the highest values of the estimated effects among all the factors investigated, having great and positive influence on the separation efficiency. By analyzing the response surface was determined maximum removal efficiency above 90% for both measured for turbidity as a measure of color when in a saline medium (30 g/L), the high oil concentrations (306 ppm) using low concentrations of de-emulsifying (1,1 ppm) and at pH close to neutral

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‖

Estudo fenomenológico e numérico do escoamento estratificado óleo-água ondulado e com mistura na interface

Escoamentos bifásicos estão presentes em diversos processos naturais e industriais, como na indústria de petróleo. Podem apresentar-se em diferentes configurações topológicas, ou, padrões de escoamento, entre eles o escoamento estratificado ondulado e o estratificado com mistura na interface. Os escoamentos bifásicos estratificados óleo-água têm sido utilizados como uma forma conveniente de evitar a formação de emulsões de água em óleo em oleodutos e possuem uma ocorrência comum em poços de petróleo direcionais. Quando a onda interfacial ultrapassa determinado limite geométrico e cinemático, surge o fenômeno do entranhamento de gotas, representado por misturas entre as fases junto à interface que promovem um aumento na queda de pressão. Modelos têm sido apresentados pela literatura na tentativa de descrever o fenômeno do entranhamento de gotas. Neste trabalho é apresentada uma nova proposta de modelagem matemática unidimensional para o entranhamento de gotas com o objetivo de melhorar a previsão dos parâmetros envolvidos, em especial, da fração volumétrica de óleo e da queda de pressão bifásica. Também foi utilizada simulação numérica computacional, CFD (Computational Fluid Dynamics), com o uso de software comercial para obtenção dos valores dos parâmetros do escoamento estratificado ondulado óleo-água (fração volumétrica de óleo, queda de pressão, amplitude e comprimento da onda interfacial). Os resultados da modelagem fenomenológica para entranhamento e os de CFD foram comparados com bancos de dados experimentais. Os resultados em CFD mostram concordância com os resultados experimentais, tanto na análise qualitativa das propriedades geométricas das ondas interfaciais, quanto na comparação direta com os dados para fração volumétrica e queda de pressão. Os resultados numéricos da modelagem fenomenológica para fatores de entranhamento apresentam boa concordância com dados da literatura.

Projeto e Operação em Escala Semi-Industrial de um Equipamento para Tratamento de Águas Produzidas na Indústria do Petróleo Utilizando Nova Tecnologia: misturador-decantador à inversão de fases - MDIF

The aim of this work is to use a new technology in the treatment of produced wastewaters from oil industry. An unit for treat produced waters called UTMDIF, was designed, installed and operated in an industrial plant for treatment of effluents from oil industry. This unit operates by means of the method of separation of phase inversion and can become a promising alternative to solve the problem of oil/water separation. This method constitutes the basis of the working of a new design of mixersettler of vertical configuration which occupies small surface area. The last characteristic becomes specially important when there is limitation on the lay-out of the plant, for example, over maritime platforms to explore oil. This equipment in a semi-industrial scale treats produced wastewaters contaminated with oil at low concentrations (ranging from 30 to 150 mg/L) and throughputs of 320 m3/d (47,4 m3 m-2 h-1). Good results were obtained in oil/water separation which leads to the necessary specification to discharge those wastewaters. Besides, the non dependence of the efficiency of separation in spite of the salinity of the medium becomes the equipment an attractive new technology to treat wastewaters containing oil at low concentrations

Tratamento de efluentes oleosos por floculação pneumática em linha e separação por flotação : processo FF

A separação/remoção de óleos emulsificados em água foi estudada, utilizando um novo processo baseado nas técnicas de floculação pneumática em linha, seguida de separação por flotação (denominado de processo de Floculação-Flotação ou processo FF). A primeira etapa do estudo foi o projeto, construção e montagem de um sistema piloto de geração de emulsões, floculação pneumática em linha e de separação por flotação, instalado no Laboratório de Águas Oleosas, na Refinaria Alberto Pasqualini (REFAP S.A.), Canoas-RS. Após esta etapa, foram realizados estudos utilizando água oleosa sintética, visando caracterizar e otimizar os principais parâmetros da floculação pneumática, fase determinante no processo FF. Os resultados mostraram que a melhor eficiência, 93 %, foi obtida quando da utilização de um floculador tipo serpentina de 20 elementos de mistura (MS-20), uma concentração de 2 mg/L de floculante (PVA) e uma vazão de ar de 40 L/min. Esta eficiência correspondeu a uma concentração residual de óleo na água tratada de 10 mg/L. Foi demonstrado ainda que, independentemente do tipo de floculador e da vazão de água oleosa, a remoção de óleo é determinada pela perda de carga resultante da injeção de ar antes do floculador. No estudo do tratamento do efluente oleoso proveniente da saída do separador PPI (REFAP S.A.), os melhores resultados foram obtidos utilizando-se o Mafloc-489 (floculante catiônico de alto peso molecular), em uma concentração de 6 mg/L, proporcionando uma concentração residual de óleo no efluente tratado de 8 mg/L (91 % de remoção) O processo de Floculação-Flotação estudado, demonstrou ser também eficiente na remoção de outros poluentes do efluente, além do óleo. Nas melhores condições operacionais, foram removidos 87 % da turbidez, 90 % dos sólidos suspensos, 91 % do óleo e 56 % da demanda química de oxigênio (DQO), proporcionando, em apenas uma etapa de tratamento, um efluente tratado com níveis de poluentes analisados abaixo do padrão exigido pelo órgão ambiental Estadual (FEPAM). Os principais mecanismos envolvidos no processo FF estão relacionados com a irreversibilidade na adsorção do polímero sob turbulência e a conformação deste na interface óleo/água/ar. O alto grau de cisalhamento, resultado dos fluxos volumétricos de ar e água, e a maior “insolubilidade” (precipitação) do polímero na interface ar/água, facilitam a geração de grandes flocos aerados de estrutura fibrosa. Esses resultados e outros obtidos com diferentes efluentes reais e suspensões sólidas mostraram que o processo FF possui um elevado potencial como nova operação unitária de separação líquido1/líquido2, sólido/líquido ou sólido/líquido1/líquido2. As principais vantagens do FF são os baixos custos envolvidos (investimento e operacional), a simplicidade dos elementos construtivos (compactos), a confiabilidade nos resultados e sua elevada capacidade de tratamento (> 60 m3/m2/h).

Remoção de óleo da água de produção por flotação em coluna utilizando tensoativos de origem vegetal

In the petroleum industry, water is always present in the reservoir formation together with petroleum and natural gas and this fact provokes the production of water with petroleum, resulting in a great environmental impact. Several methods can be applied for treatment of oily waters, such as: gravitational vases, granulated media filtration systems, flotation process, centrifugation process and the use of hydrocyclones, which can also be used in a combined way. However, the flotation process has showed a great efficiency as compared with other methods, because these methods do not remove great part of the emulsified oil. In this work was investigated the use of surfactants derived from vegetable oils, OSS and OGS, as collectors, using the flotation process in a glass column with a porous plate filter in its base for the input of the gaseous steam. For this purpose, oil/water emulsions were prepared using mechanical stirring, with concentrations around 300 ppm. The air flow rate was set at 700 cm3/min and the porous plate filter used for the generation of the air bubbles has pore size varying from 16 to 40 Pm. The column operated at constant volume (1500mL). A new methodology has been developed to collect the samples, where, instead of collecting the water phase, it was collected the oil phase removed by the process in the top of the flotation column. It has been observed that it is necessary to find an optimum surfactant concentration to achieve enhanced removal efficiency. Being for OSS 1.275 mmol/L and for OGS 0.840 mmol/L, with removal efficiencies of 93% and 99%, respectively, using synthetic solutions. For the produced water, the removal in these concentrations was 75% for OSS and 65% for OGS. It is possible to remove oil from water in a flotation process using surfactants of high HLB, fact that is against the own definition of HLB (Hydrophile-Lipophile Balance). The interfacial tension is an important factor in the oil removal process using a flotation process, because it has direct interference in the coalescence of the oil drops. The spreading of the oil of the air bubble should be considered in the process, and for the optimum surfactant concentrations it reached a maximum value. The removal kinetics for the flotation process using surfactants in the optimum concentration has been adjusted according to a first order model, for synthetic water as for the produced water.

Development and characterization of lipid-based nanosystems for controlled release of bioactive compounds

Tese de Doutoramento em Engenharia Química e Biológica.

Aperfeiçoamento no projeto de um protótipo de misturador-decantador à inversão de fases visando aplicação na indústria do petróleo

In the oil industry the mixture oil/water occurs in the operations of production, transportation and refining, as well as during the use of its derivatives. The amount of water produced associated with the oil varies and can reach values of 90% in volume in the case of mature phase of the production fields. The present work deals with the development of new design of the Mixer Settler based on Phase Inversion (MDIF) in a laboratory scale. We envisage this application in industrial scale so the phases of project, construction and operation are considered. The modifications most significant, in comparison with the original prototype, include the materials of construction and the substitution of the equipment used in the mixing stage of the process. It was tested the viability of substitution of the original system of mechanical mixing by a static mixer. A statistical treatment by means of an experimental design of composed central type was used in order to evaluate the behavior of the main variables of the separation process as function of the efficiency of separation for the new device. This procedure is useful to delimit an optimal region of operation with the equipment. The variables of process considered on the experimental design were: oil concentration in the feeding water (mg/L); Total volumetric flow rate (L/h); Ratio organic/water on volumetric basis (O/A). The separation efficiency is calculated by comparison of the content of oil and greases in the inlet and outlet of the equipment. For determination of TOG (Total Oil and Grease), the method used was based in the absorption of radiation in the infra-red region. The equipment used for these determinations was InfraCal® TOG/TPH Model HATR-T2 of the Wilks Enterprise, Incorporation. It´s important to stand out that this method of measure has being used by PETROBRAS S.A. Results of global efficiency of separation oil/water varied from 75.3 to 97.7% for contaminated waters containing up to 1664,1 mg/L of oil. By means of tests carried out with a real sample of contaminated water supplied by PETROBRAS we have got an effluent specified in terms of the legal standards required for discharging. Thus, the new design of equipment constitutes a real alternative for the conventional systems of treatment of produced water in the oil industry

Determinação estatística dos contatos fluidos em perfis de poço

No interior dos reservatórios petrolíferos, o efeito da gravidade produz naturalmente a segregação dos fluidos presentes. Em razão basicamente das forças capilares não existe uma superfície definida de separação entre cada dois fluidos. No entanto, é comum na engenharia de petróleo admitir-se uma superfície convencional de separação dos fluidos. À essa superfície dá-se o nome de interface fluida ou contato fluido. A obtenção da localização dos contatos fluidos no interior dos reservatórios, como os contatos óleo-água, contatos gás-água e os contatos gás-óleo, sem a interpretação completa dos perfis geofísicos ou a realização dos procedimentos diretos dos testes de formação é um problema de difícil solução para a indústria do petróleo. O posicionamento em profundidade dos contatos pode ser utilizado para a definição dos procedimentos de completação do poço e para o posicionamento do canhoneio nos horizontes produtores dos poços verticais. Temos também a aplicação do mapeamento deste parâmetro, para os projetos e controle da perfuração no caso dos poços direcionais e horizontais, que utilizam tal informação para o posicionamento do eixo do poço no interior da zona de hidrocarboneto no reservatório, a fim de se evitar, principalmente, a produção de água. Este trabalho apresenta uma metodologia para a identificação e posicionamento dos contatos fluidos, através da aplicação da técnica da estatística multivariada, chamada de análise discriminante. Nesta aplicação, faz-se uso direto dos perfis de resistividade (R_T), de raios gama natural (RG), de densidade (ρ_b), de porosidade neutrônica (Φ_N), de caliper (Cal) e do perfil de volume de argila (Vcla), como dados de entrada no programa de análise discriminante. Para o caso de depósitos clásticos, com seqüências arenito-folhelho, a análise discriminante fornece ainda a indicação da litologia e as espessuras aparentes dos reservatórios. As curvas de perfis geofísicos aplicadas para a avaliação desta metodologia são provenientes de poços perfurados na bacia do lago Maracaibo, na Venezuela, onde, segundo estudos geológicos, existe a ocorrência de seqüências estratigráficas, com camadas de folhelhos e arenitos, sendo também confirmada a presença de hidrocarbonetos nos poços utilizados neste trabalho.

Tensoativo derivado do ácido cítrico: síntese e aplicação em fluidos de perfuração de emulsão inversa

This work describes the synthesis and study of the application of a new surfactant (Triester Lipophilic – TEL) obtained by citric acid with octanol. It is reaction was followed by thin layer chromatography (TLC) and after purification the product was characterized by proton and 13 – carbon nuclear magnetic resonance spectroscopy ( H and 13C NMR), thermogravimetric analysis (TGA) and surface tension analysis of oil-in-water emulsions. The TEL performance as surfactant in ester, n-paraffin and biodiesel based drilling fluids on the 70/30 and 60/40 water- oil rations (WOR) was evaluated by comparative tests of two commercial products used in the fields. These drilling fluids were aged in roller oven at 200 0 F during 16 h. The rheological and electric stability measurements were carried out at 135 ºF, the phase separation was evaluated after seven days at rest and the filtrate volume of drilling fluids was determined at high temperature and high pressure. The rheological behavior of the drilling fluids was evaluated by the flow curves. The results showed that the drilling fluids studied here presented Binghamian behavior as well as the used in the oil fields. The laboratory tests showed that the TEL reduced the filtrate volume and promoted the enhance of the thermal and mechanical stabilities.

Medicao do impacto da irrigacao gota a gota no ambiente - Salinidade

Para dar continuidade ao estudo de avaliação do impacto do sistema de rega gota a gota no meio ambiente, foram colhidas 43 amostras de solos e 24 de águas, nas parcelas dos agricultores beneficiários dos projectos financiados pela ACDI/VOCA (Agricultural Cooperative Development International et Volunteers in Overseas Cooperative Assistance) na ilha de Santiago, e analisadas no Laboratório de Análise de Solos, Águas e Plantas (LASAP) do INIDA. Foram apr0esentados os resultados de análise do pH e da condutividade eléctrica (ECW), enquanto que os do azoto (N), do fósforo (P), do potássio (K), do magnésio (Mg) e do cálcio (Ca) serão apresentados posteriormente. Segundo esses resultados e, baseado na tabela de classificação de salini0dade do solo (INIDA, 1997), 65% dos solos analisados, situadas em Librão, Cidade Velha, Cabeça d'Horta, Pico Leão, Água de Gato, Chã de Vaca, Principal, São Francisco, Laje/Órgãos, Pó de Saco, Flamengos, Calhetona, Praia Formosa, são considerados sem efeito salino ou muito pouco salino; enquanto 24% das amostras localizadas em Praia Baixo, Castelinho e Cumba Baixo são solos considerados pouco a moderadamente salinos. Por outro lado encontramos que 11% dos solos analisados (situados em Baía e Achada Baleia) são classificados de fortemente a muito fortemente salinos. O alto teor de sais encontrado, nestes solos, poderá advir do efeito da intrusão salina e da maresia, adjuvada da aplicação de fertilizantes, assim como da má qualidade da água utilizada na rega. Recomenda-se, análises de solos periódicas, assim como a elaboração de um programa de fertilização racional. Comparando os resultados das análises do solo realizadas em 2002, encontramos que em 2004 houve um aumento substancial nos valores da condutividade eléctrica do solo. O pH do solo apresentou-se sem grandes variações (7,6 a 7,9), estando dentro dos valores encontrados para a maioria dos solos em Cabo Verde (Neutro a ligeiramente alcalino). 88 % das amostras de água dos furos, dos poços e das nascentes são classificados de boa qualidade (29%) e permissível (59%) para a rega, e não representam grandes riscos na salinização dos solos. O furo FT-44, na zona de Baía, carece de um cuidado especial na exploração e utilização da água para a rega. Pois, um controle dos pontos de água é fundamental para evitar a sobre-exploração e consequentemente a salinização dos mesmos. Alertamos, ainda, aos responsáveis dos serviços de água, da necessidade urgente de reavaliar a exploração do furo (FT-26) em Achada Baleia e o poço (P – 55-587) em Cassunda – Cumba, pelo facto de apresentarem valores elevados de condutividade eléctrica (3760 a 5550 S/cm), considerados de má qualidade para a rega.

Sistemas microemulsionados como carreador lipídico para fármacos insolúveis

Several pharmaceutical products have been developed in recent years aiming to enhance the treatment of diseases by increasing the effectiveness of drugs. Many of these new products are based on new drug delivery systems. Among these, microemulsions, which were first studied in 1943 by Hoar and Schulman, is of great interest. Microemulsion can be defined as a thermodynamically stable, isotropic, translucent and transparent system of two immiscible liquids stabilized by a surfactant film located in the oil / water interface. The aim os this work was the incorporation of Amphotericin B and Simvasatin to a microemulsion system and analyzes its physicochemical properties and their therapeutical activity when incorporated into this system. Some very promising results were achieved as the reduction of the toxicity and maintenance of the efficacy of the Amphotericin B incorpored into a microemulsion, which was demonstrated in the in vitro pharmacotoxicological study. As for the incorporation of Simvastatin in microemulsion, it was observed a significant improvement in the potential antiinflammatory and anti-infective properties when the system was use to treat infected wounds (simvastatin pleiotropic effects). Therefore, it can be concluded that the incorporation of these drugs into microemulsion system reveal the potential of microemulsions as a promising and novel dosage form, qualifying them for future trials in order to make them available in the pharmaceutical market

Utilização do éster de soja como biolubrificante

The lubricants found in the market are of mineral or synthetic origin and harm to humans and the environment, mainly due to their improper discard. Therefore industries are seeking to develop products that cause less environmental impact, so to decrease mainly, operator aggression the Cutting Fluids became an emulsion of oil / water or water / oil. However, the emulsion was not considered the most suitable solution for environmental question, therefore the search for biodegradable lubricants and which no are toxic continues and so vegetable oils are seen, again, as a basis for the production of lubricants. The biggest problem with these oils is their oxidative instability that is intensified when working at high temperatures. The process transesterification decreases the oxidation, however changes some physical and chemical properties. Therefore soybean oil after the transesterification process was subjected to tests of density, dynamic viscosity, kinematic viscosity which is calculated from two parameters mentioned, flash point and acidity. Besides the physico-chemical test the soybean oil was subjected to a dynamic test in a tribometer adapted from a table vise, whose induced wear was the adhesive and ultimately was used as cutting fluid in a process of turning in two different materials, steel 1045 and cast iron. This latter test presented results below the mineral cutting fluid which it was compared in all tests, already in other experiments the result was satisfactory and other experiments not, so that chemical additives can be added to the oil analyzed to try equate all parameters and so formulate a biolubrificante not toxic to apply in machining processes of metalworking industry