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‖

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

Avaliação do método de Iwatsu et al., (1981) para isolamento de leveduras negras do solo, degradadoras de hidrocarbonetos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Micro-fungos de interesse para o setor de petróleo, gás e biocombustíveis

Oil is a hydrocarbon mixture of various sizes, including saturated and aromatic compounds. Natural gas is a mixture of gaseous hydrocarbons and its main component is methane. In our society, the great demand for these fuels requires fast extraction, transportation and refining, increasing the number of accidents that compromise the environment. Oil is a finite resource and it is necessary to reduce the problems related to the question concerning environmental pollution which has encouraged the search for alternative fuel sources in our country. So today we have two major biofuels: ethanol and biodiesel. Concurrently, many studies have been done directed toward the isolation of microorganisms capable of degrading petrochemical industrial wastes, most of them using as a source of isolation soil and water collected in a contaminated environment. Isolation from alternative substrates has emerged as a new strategy that has provided satisfactory results. In this work, we present the leaf-cutter ants of the Attini tribe as a source for the isolation of micro-fungi with the potential for hydrocarbon degradation. These insects have a social way of life and a highly specialized system of intra and interspecific communication, which is based on the recognition of individuals through volatile chemical compounds, the majority hydrocarbons, stored in their exoskeleton. The micro-environment exoskeleton of Attini ants (genus Atta) used in this work proved to be a rich source of microbial biodiversity, as other studies have found. The flotation isolation technique applied here allowed the achievement of 214 micro-fungi, 118 representatives of the dematiaceous fungi group and 96 hyaline filamentous fungi. They were submitted to toluene degradation tests and at least one strain of each genus presented good results, namely Teratosphaeria, Exophiala, Cladosporium, Penicillium, Aspergillus... (Complete abstract click electronic access below)

Fungos fitopatógenos associados às formigas cortadeiras (Formicidae: Tribo Attini)

The ants of genus Atta belong to the Attine tribe (order Hymenoptera, family Formicidae, subfamily Myrmicinae) and are commonly known as leaf-cutting ants for having the habit of cutting several vegetable species used as substrate for growing mutualistic fungus (Agaricales: Lepiotaceae). Recent studies showed that, in addition to that, other fungi may occur in the nests in a dorment state or participate in the functioning dynamic of this symbiosis. Researches related to surveys of fungus biodiversity in nests of different Atta species have found important phytopathogenic representatives. In Brazil, studies about integrated management of plagues, developed by Embrapa Meio Ambiente (Embrapa Environment), point out the need of higher investments in projects that involve the phytopathogenic transmission by insects in order to reduce costs to control them or minimize environmental impact. The purpose of this study was to broaden the knowledge about the ecology of these fungi, isolating and identifying species associated with Attine tribe ants, thus understanding the scope of pathogenic and phytopathogenic species spread by these ants. For that reason, gynes were collected from Atta laevigata and Atta capiguara anthills located at Unesp Botucatu (São Paulo, Brazil) campus. In order to isolate the fungus, the mineral oil floating technique was used. The identification of the isolated fungi was done based on microscopic and molecular characteristics using DNA ribosomal sequencing. The most highly abundant genera found so far were: Cladosporium, Exophiala, Penicillium, Acremonium, Phialophora and Teratosphaeria. Representatives of the genera Exophiala, Phialophora and Cladosporium may be human pathogens, whereas Teratosphaeria and Penicillium are related to diseases in Eucalyptus and citric fruits, respectively. The results show that these ants may host important fungal species besides the ones already... (Complete abstract click electronic access below)

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.

Modelagem da transferência de massa na remoção do óleo da água produzida por flotação em coluna com uso de tensoativos de origem vegetal

The treatment of oil produced water and its implications are continually under investigation and several questions are related to this subject. In the Northeast Region Brazil, the onshore reservoirs are, in its majority, mature oil fields with high production of water. As this oil produced water has high levels of oil, it cannot be directly discarded into the environment because it represents a risk for contamination of soil, water, and groundwater, or even may cause harm to living bodies. Currently, polyelectrolytes that promote the coalescence of the oil droplets are used to remove the dispersed oil phase, enhancing the effectiveness of the flotation process. The non-biodegradability and high cost of polyelectrolytes are limiting factors for its application. On this context, it is necessary to develop studies for the search of more environmentally friendly products to apply in the flotation process. In this work it is proposed the modeling of the flotation process, in a glass column, using surfactants derived from vegetal oils to replace the polyelectrolytes, as well as to obtain a model that represents the experimental data. In addition, it was made a comparative study between the models described in the literature and the one developed in this research. The obtained results showed that the developed model presented high correlation coefficients when fitting the experimental data (R2 > 0.98), thus proving its efficiency in modeling the experimental data.

Tratamento de águas oleosas oriundas do processo de produção de óleo de dendê utilizando a flotação por ar dissolvido

This study was developed to evaluate the performance of different coagulant and pH dosages by applying the use of Dissolved Air Flotation (FAD) to enable its use in effluent treatment of the extraction process of palm oil. The study was developed in the laboratory, where studies about emulsions stability were made for the production of a synthetic effluent which best suit the characteristics of raw effluent. The synthetic water that would be used in the tests of FAD was produced, once the stability and characterization which best approached the raw wastewater was obtained. Trials tested three coagulant doses, combined with various pH ranges and five upward velocities (Va), finding an optimal range of this combination. Some operating parameters such as time and gradient of rapid mixing (20 s / 1000 s-1), time and gradient flotation (15 min / 60 s-1), chamber pressure saturation (450 kPa) and recirculation rate (20%) were set. In this way, samples were collected for analysis of the removal of turbidity parameters, suspended solids and oils and greases. This one is obtained by a correlation turbidity x oils and greases, referring to the previous analysis. The degree of removal obtained were 73,97% for turbidity, 51,4% for total suspended solids and 86,2% for oils and greases. Removal rates may be increased in later studies, by ranging the velocity gradient and flocculation parameters and the recirculation ratio, and by using lower flotation speeds to these effluent characteristics.

Remoção de óleos emulsificados por flotação por ar dissolvido

Neste trabalho estuda-se o processo de flotação por ar dissolvido (FAD) como método de remoção de óleos emulsificados. Realizou-se uma revisão bibliográfica tanto do processo de flotação como dos fundamentos físico-químicos envolvidos na estabilidade e flotação de emulsões. Foram realizados testes de estabilidade de emulsões, de FAD descontínuos e contínuos, utilizando-se emulsões de 1000 mg/l de Óleo diesel e heptano. Verificou-se a eficiência do sulfato de alumínio e de compostos poliméricos como agentes desestabilizantes. Estudou-se a influência do tipo e concentração dos agentes desestabilizantes, pH da emulsão, do tipo de água e agitação nos testes de estabilidade como também na flotação por ar dissolvido. Os resultados obtidos indicaram a viabilidade técnica da aplicação do processo para a clarificação de efluentes oleosos atingindo valores de turbidez residual satisfatórios (menores que 5 UNT). O sulfato de alumínio mostrou-se mais eficiente como agente desestabilizante de ambas emulsões nos estudos de estabilidade e testes de PAD descontínuos, mas o polímero catiônico C-505 apresentou melhores resultados nos testes de flotação contínuos. O presente trabalho ainda apresenta um estudo de dimensionamento e do custo da unidade de FAD para remoção de óleos emulsificados que leva em consideração os custos de investimentos e de operação da unidade. Verifica-se que o custo total da unidade depende da vazão de alimentação, taxa de recirculação, taxa ar/sólido em massa e concentração inicial de óleos. Conclui-se que para as taxas de ar/sólido usados na indústria (geralmente menores que 0,1) o custo operacional do reagente é o parâmetro determinante do custo total atualizado da unidade. Isto faz com que o custo total atualizado seja essencialmente independente da relação taxa de aplicação - taxa ar/sólido.

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).

Projeto, construção e análise de um prototipo vibracional em escala de bancada aplicável ao tratamento de água de produção de petróleo bruto, mediante inovadora operação híbrida de adsorção e auto-flotação

A self-flotator vibrational prototype electromechanical drive for treatment of oil and water emulsion or like emulsion is presented and evaluated. Oil production and refining to obtain derivatives is carried out under arrangements technically referred to as on-shore and off-shore, ie, on the continent and in the sea. In Brazil 80 % of the petroleum production is taken at sea and area of deployment and it cost scale are worrisome. It is associated, oily water production on a large scale, carrier 95% of the potential pollutant of activity whose final destination is the environment medium, terrestrial or maritime. Although diversified set of techniques and water treatment systems are in use or research, we propose an innovative system that operates in a sustainable way without chemical additives, for the good of the ecosystem. Labyrinth adsor-bent is used in metal spirals, and laboratory scale flow. Equipment and process patents are claimed. Treatments were performed at different flow rates and bands often monitored with control systems, some built, other bought for this purpose. Measurements of the levels of oil and grease (OGC) of efluents treaty remained within the range of legal framework under test conditions. Adsorbents were weighed before and after treatment for obtaining oil impregna-tion, the performance goal of vibratory action and treatment as a whole. Treatment technolo-gies in course are referenced, to compare performance, qualitatively and quantitatively. The vibration energy consumption is faced with and without conventional flotation and self-flotation. There are good prospects for the proposed, especially in reducing the residence time, by capillary action system. The impregnation dimensionless parameter was created and confronted with consecrated dimensionless parameters, on the vibrational version, such as Weber number and Froude number in quadratic form, referred to as vibrational criticality. Re-sults suggest limits to the vibration intensity

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

Integração dos processos de flotação e foto-fenton para redução de óleos e graxas de água produzida em campos de petróleo

During production of oil and gas, there is also the production of an aqueous effluent called produced water. This byproduct has in its composition salts, organic compounds, gases and heavy metals. This research aimed to evaluate the integration of processes Induced Air Flotation (IAF) and photo-Fenton for reducing the Total Oils and Greases (TOG) present in produced water. Experiments were performed with synthetic wastewater prepared from the dispersion of crude oil in saline solution. The system was stirred for 25 min at 33,000 rpm and then allowed to stand for 50 min to allow free oil separation. The initial oil concentration in synthetic wastewater was 300 ppm and 35 ppm for the flotation and the photo-Fenton steps, respectively. These values of initial oil concentration were established based on average values of primary processing units in Potiguar Basin. The processes were studied individually and then the integration was performed considering the best experimental conditions found in each individual step. The separation by flotation showed high removal rate of oil with first-order kinetic behavior. The flotation kinetics was dependent on both the concentration and the hydrophilic-lipophilic balance (HLB) of the surfactant. The best result was obtained for the concentration of 4.06.10-3 mM (k = 0.7719 min-1) of surfactant EO 2, which represents 86% of reduction in TOG after 4 min. For series of surfactants evaluated, the separation efficiency was found to be improved by the use of surfactants with low HLB. Regarding the TOG reduction step by photo-Fenton, the largest oil removal reached was 84% after 45 min of reaction, using 0.44 mM and 10 mM of ferrous ions and hydrogen peroxide, respectively. The best experimental conditions encountered in the integrated process was 10 min of flotation followed by 45 min of photo-Fenton with overall TOG reduction of 99%, which represents 5 ppm of TOG in the treated effluent. The integration of processes flotation and photo-Fenton proved to be highly effective in reducing TOG of produced water in oilfields

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.

Avaliação de floculante natural à base de Moringa oleifera no tratamento de água produzida na indústria do petróleo: aplicação da técnica combinada floculação/flotação

The principal effluent in the oil industry is the produced water, which is commonly associated to the produced oil. It presents a pronounced volume of production and it can be reflected on the environment and society, if its discharge is unappropriated. Therefore, it is indispensable a valuable careful to establish and maintain its management. The traditional treatment of produced water, usualy includes both tecniques, flocculation and flotation. At flocculation processes, there are traditional floculant agents that aren’t well specified by tecnichal information tables and still expensive. As for the flotation process, it’s the step in which is possible to separate the suspended particles in the effluent. The dissolved air flotation (DAF) is a technique that has been consolidating economically and environmentally, presenting great reliability when compared with other processes. The DAF is presented as a process widely used in various fields of water and wastewater treatment around the globe. In this regard, this study was aimed to evaluate the potential of an alternative natural flocculant agent based on Moringa oleifera to reduce the amount of oil and grease (TOG) in produced water from the oil industry by the method of flocculation/DAF. the natural flocculant agent was evaluated by its efficacy, as well as its efficiency when compared with two commercial flocculant agents normally used by the petroleum industry. The experiments were conducted following an experimental design and the overall efficiencies for all flocculants were treated through statistical calculation based on the use of STATISTICA software version 10.0. Therefore, contour surfaces were obtained from the experimental design and were interpreted in terms of the response variable removal efficiency TOG (total oil and greases). The plan still allowed to obtain mathematical models for calculating the response variable in the studied conditions. Commercial flocculants showed similar behavior, with an average overall efficiency of 90% for oil removal, however it is the economical analysis the decisive factor to choose one of these flocculant agents to the process. The natural alternative flocculant agent based on Moringa oleifera showed lower separation efficiency than those of commercials one (average 70%), on the other hand this flocculant causes less environmental impacts and it´s less expensive