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.

Extração do corante reactive blue 19 utilizando tensoativo não iônico

The generation of effluent from the finishing process in textile industry is a serious environmental problem and turned into an object of study in several scientific papers. Contamination with dyes and the presences of substances that are toxic to the environment characterize this difficult treatment effluent. Several processes have already been evaluated to remove and even degrade such pollutants are examples: coagulation-flocculation, biological treatment and advanced oxidative processes, but not yet sufficient to enable the recovery of dye or at least of the recovery agent. An alternative to this problem is the cloud point extraction that involves the application of nonionic surfactants at temperatures above the cloud point, making the water a weak solvent to the surfactant, providing the agglomeration of those molecules around the dyes molecules by affinity with the organic phase. After that, the formation of two phases occurred: the diluted one, poor in dye and surfactant, and the other one, coacervate, with higher concentrations of dye and surfactants than the other one. The later use of the coacervate as a dye and surfactant recycle shows the technical and economic viability of this process. In this paper, the cloud point extraction is used to remove the dye Reactive Blue from the water, using nonionic surfactant nonyl phenol with 9,5 etoxilations. The aim is to solubilize the dye molecules in surfactant, varying the concentration and temperature to study its effects. Evaluating the dye concentration in dilute phase after extraction, it is possible to analyze thermodynamic variables, build Langmuir isotherms, determine the behavior of the coacervate volume for a surfactant concentration and temperature, the distribution coefficient and the dye removal efficiency. The concentration of surfactant proved itself to be crucial to the success of the treatment. The results of removal efficiency reached values of 91,38%, 90,69%, 89,58%, 87,22% and 84,18% to temperatures of 65,0, 67,5, 70,0, 72,5 and 75,0°C, respectively, showing that the cloud point extraction is an efficient alternative for the treatment of wastewater containing Reactive Blue

Estudo dos parâmetros de extração de fenol de efluentes aquosos por um tensoativo não iônico

Environmental sustainability has become one of the topics of greatest interest in industry, mainly due to effluent generation. Phenols are found in many industries effluents, these industries might be refineries, coal processing, pharmaceutical, plastics, paints and paper and pulp industries. Because phenolic compounds are toxic to humans and aquatic organisms, Federal Resolution CONAMA No. 430 of 13.05.2011 limits the maximum content of phenols, in 0.5 mg.L-1, for release in freshwater bodies. In the effluents treatment, the liquid-liquid extraction process is the most economical for the phenol recovery, because consumes little energy, but in most cases implements an organic solvent, and the use of it can cause some environmental problems due to the high toxicity of this compound. Because of this, exists a need for new methodologies, which aims to replace these solvents for biodegradable ones. Some literature studies demonstrate the feasibility of phenolic compounds removing from aqueous effluents, by biodegradable solvents. In this extraction kind called "Cloud Point Extraction" is used a nonionic surfactant as extracting agent of phenolic compounds. In order to optimize the phenol extraction process, this paper studies the mathematical modeling and optimization of extraction parameters and investigates the effect of the independent variables in the process. A 32 full factorial design has been done with operating temperature and surfactant concentration as independent variables and, parameters extraction: Volumetric fraction of coacervate phase, surfactant and residual concentration of phenol in dilute phase after separation phase and phenol extraction efficiency, as dependent variables. To achieve the objectives presented before, the work was carried out in five steps: (i) selection of some literature data, (ii) use of Box-Behnken model to find out mathematical models that describes the process of phenol extraction, (iii) Data analysis were performed using STATISTICA 7.0 and the analysis of variance was used to assess the model significance and prediction (iv) models optimization using the response surface method (v) Mathematical models validation using additional measures, from samples different from the ones used to construct the model. The results showed that the mathematical models found are able to calculate the effect of the surfactant concentration and the operating temperature in each extraction parameter studied, respecting the boundaries used. The models optimization allowed the achievement of consistent and applicable results in a simple and quick way leading to high efficiency in process operation.

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

Preparo de amostras e métodos para a determinação do teor de óleo essencial de frutos de limoeiro

Objetivou-se avaliar alternativas de preparo da amostra e os métodos quantitativos para a determinação do teor de óleo em frutos de limão. Os tratamentos foram avaliados por meio do delineamento estatístico inteiramente casualizado, em esquema fatorial 2x2x6, com quatro repetições, sendo duas variedades-copa de limoeiro verdadeiro ('Siciliano' e 'Eureka'), dois métodos analíticos para a determinação do teor de óleo (Scott e Clevenger) e seis formas de preparo dos frutos para análise (análise do fruto inteiro; frutos cortados na longitudinal e análise de ¼; frutos cortados na longitudinal e análise de ¹/2; frutos cortados ao meio e análise da parte superior; frutos cortados ao meio e análise da parte inferior; e análise de ²/8 do fruto). O método denominado de Clevenger foi o mais eficiente na determinação do teor de óleo essencial, e as formas de preparo de amostras ½ inferior, ½ superior, ¼ longitudinal e ½ longitudinal dos frutos proporcionaram valores superiores de óleo essencial.

Equilíbrio líquido-líquido para o sistema biodiesel de óleo de semente de melão (Cucumis melo l.) + metanol + glicerina

Rio Grande do Norte, northeast state from Brazil, it is the greatest producer and exporter of yellow melon, well known as Spanish melon. Despite the consumption of this fruit to be mainly its pulp, melon seeds are an important source of lipids considered an industrial residue it has been discharge product. The use of oilseeds in order to produce biodiesel establishes an important raw material and the increase of its production promotes the national development of the agriculture. In this background, the aim of this work has been to use oil from seeds of yellow melon to produce biodiesel and to accomplish a study of the phase equilibrium of the system evolving biodiesel, methanol and glycerin. The biodiesel was obtained by oil transesterification through methylic route with molar ratio 1:9.7 (oil:alcohol) and with a mass of NaOH of 0.5% from the oil mass; the reaction time was 73 minutes at 55 °C. A yield of 84.94% in biodiesel was achieved. The equilibria data present a well-characterized behavior with a great region of two phases. The tie lines indicate that methanol has a best solubility in the phase that is rich in glycerin. Consistency of the experimental data was made based on Othmer-Tobias and Hand correlations which values above 0.99 were found to correlation coefficients, this fact confers a good thermodynamic consistency to the experimental data. NRTL and UNIQUAC models were employed to predict liquid-liquid equilibrium of this system. It was observed a better concordance of the results when NRTL was applied (standard deviation 1.25%) although the UNIQUAC model has presented a quite satisfactory result either (standard deviation 2.70%). The NRTL and UNIQUAC models were also used to evaluate the effect of temperature in the range of 328 K to 358 K, in which a little change in solubility with respect to the data obtained at 298 K was observed, thus being considered negligible the effect of temperature

Estudo de sistemas microemulsionados utilizando água do mar na recuperação avançada de petróleo

Petroleum exists in the nature in certain underground formations where it is adsorbed into the rocks pores. For the conventional recovery methods usually only 30% of the oil is extracted and this can be credited, basically, to three aspects: high viscosity of the oil, geology of the formation and high interfacial tensions between the reservoir s fluids. The enhanced recovery methods use the injection of a fluid or fluids mixture in a reservoir to act in points where the conventional process didn't reach the recovery rates. Microemulsion flooding, considered an enhanced method, has the purpose to desorb the oil from the rock formation and to attain an efficient displacement of the oil emulsion. With this in mind, this work was accomplished with two main objectives: the study of the parameters effect that influence a microemulsified system (surfactant and cosurfactant types, C/S rate and salinity) and the evaluation of displacement efficiency with the microemulsions that showed stability in the rich aqueous area. For the analyzed parameters it was chose the microemulsions composition used in the recovery stage: 25% water, 5% kerosene, 46.7% of butanol as cosurfactant and 23.3% of BC or SCO cosurfactant. The core plugs of Assu and Botucatu sandstones were appraised in porosity and permeability tests and then submitted to the steps of saturation with seawater and oil, conventional recovery with water and enhanced recovery with the selected microemulsions. The Botucatu sandstone presented better recovery parameters, and the microemulsion composed with BS surfactant had larger recovery efficiency (26.88%)

Extração, caracterização e aplicação do corante de urucum (Bixa orellana L.) no tingimento de fibras naturais

The increasing demand for natural dyes in place of synthetic ones is justified by the non-toxicity or low toxicity of the former. The synthetic dyes are associated with diseases like cancer as well as when released in the environment takes longer to degrade and the intermediates could be still more toxic. The Annatto (Bixa Orellana L.) is a carotenoid and one of the more important natural dyes used in the food industry. In the form of dye, it represents nearly 70% of the world natural dye production and 90% in Brazil. In the present work, annatto seeds were used of the species peruana paulista, which had nearly 2.1% of bixin. The process of dye extraction with ethyl alcohol showed 4% of dye in the form of powder with particle diameter of 28mm. The extraction process did not alter the chemical composition of the dye, which was confirmed by the electronic spectrum of absorption. Dyeings were carried out with different mordents to study the total colour difference as well as the wash fastness properties and friction fastness properties under wet and dry conditions. The samples treated with copper sulphate showed colour difference but at the same time showed better fastness results. The samples treated with resin (no formaldehyde) did not alter the colour significantly still better the fastness properties. From the results, it could be stated that the resin could be an alternative for heavy metallic mordents

Microemulsões aplicadas ao tratamento de Óleos isolantes

Naphthenic lubricating oils are used in transformers with the purpose of promoting electrical insulation and dissipating heat. The working temperature range of these oils typically lies between 60°C and 90°C and their useful life is 40 years in average. In that temperature range, the oils are decomposed during operation, whereby a small fraction of polar compounds are formed. The presence of these compounds may induce failure and loss of physical, chemical and electrical properties of the oil, thus impairing the transformer operation. By removing these contaminants, one allows the oxidized insulating oil to be reused without damaging the equipment. In view of this, an investigation on the use of surfactants and microemulsions as extracting agents, and modified diatomite as adsorbent, has been proprosed in this work aiming to remove polar substances detected in oxidized transformer oils. The extraction was carried out by a simple-contact technique at room temperature. The system under examination was stirred for about 10 minutes, after which it was allowed to settle at 25°C until complete phase separation. In another experimental approach, adsorption equilibrium data were obtained by using a batch system operating at temperatures of 60, 80 and 100°C. Analytical techniques involving determination of the Total Acidity Number (TAN) and infrared spectrophotometry have been employed when monitoring the decomposition and recovery processes of the oils. The acquired results indicated that the microemulsion extraction system comprising Triton® X114 as surfactant proved to be more effective in removing polar compounds, with a decrease in TAN index from 0.19 to 0.01 mg KOH/g, which is consistent with the limits established for new transformer oils (maximal TAN = 0.03 mg KOH/g). In the adsorption studies, the best adsorption capacity values were as high as 0.1606 meq.g/g during conventional adsoprtion procedures using natural bauxite, and as high as 0.016 meq.g/g for the system diatomite/Tensiofix® 8426. Comparatively in this case, a negative effect could be observed on the adsorption phenomenon due to microemulsion impregnation on the surface of the diatomite

Estudo da recuperação de óleo por drenagem gravitacional assistida por injeção de vapor

Steam assisted gravity drainage process (SAGD) involves two parallel horizontal wells located in a same vertical plane, where the top well is used as steam injector and the bottom well as producer. The dominant force in this process is gravitational. This improved oil recovery method has been demonstrated to be economically viable in commercial projects of oil recovery for heavy and extra heavy oil, but it is not yet implemented in Brazil. The study of this technology in reservoirs with characteristics of regional basins is necessary in order to analyze if this process can be used, minimizing the steam rate demand and improving the process profitability. In this study, a homogeneous reservoir was modeled with characteristics of Brazilian Northeast reservoirs. Simulations were accomplished with STARS , a commercial software from Computer Modelling Group, which is used to simulate improved oil recovery process in oil reservoirs. In this work, a steam optimization was accomplished in reservoirs with different physical characteristics and in different cases, through a technical-economic analysis. It was also studied a semi-continuous steam injection or with injection stops. Results showed that it is possible to use a simplified equation of the net present value, which incorporates earnings and expenses on oil production and expenses in steam requirement, in order to optimize steam rate and obtaining a higher net present value in the process. It was observed that SAGD process can be or not profitable depending on reservoirs characteristics. It was also obtained that steam demand can still be reduced injecting in a non continuous form, alternating steam injection with stops at several time intervals. The optimization of these intervals allowed to minimize heat losses and to improve oil recovery

Preparação de poliuretana à base de óleo de mamona

Polyurethanes are very versatile macromolecular materials that can be used in the form of powders, adhesives and elastomers. As a consequence, they constitute important subject for research as well as outstanding materials used in several manufacturing processes. In addition to the search for new polyurethanes, the kinetics control during its preparation is a very important topic, mainly if the polyurethane is obtained via bulk polymerization. The work in thesis was directed towards this subject, particularly the synthesis of polyurethanes based castor oil and isophorone diisocianate. As a first step castor oil characterized using the following analytical methods: iodine index, saponification index, refraction index, humidity content and infrared absorption spectroscopy (FTIR). As a second step, test specimens of these polyurethanes were obtained via bulk polymerization and were submitted to swelling experiments with different solvents. From these experiments, the Hildebrand parameter was determined for this material. Finally, bulk polymerization was carried out in a differential scanning calorimetry (DSC) equipment, using different heating rates, at two conditions: without catalyst and with dibutyltin dilaurate (DBTDL) as catalyst. The DSC curves were adjusted to a kinetic model, using the isoconversional method, indicating the autocatalytic effect characteristic of this class of polymerization reaction

Bio-óleo e biogás da degradação termoquímica de lodo de esgoto doméstico em cilindro rotativo

The objective of this study was to produce biofuels (bio-oil and gas) from the thermal treatment of sewage sludge in rotating cylinder, aiming industrial applications. The biomass was characterized by immediate and instrumental analysis (elemental analysis, scanning electron microscopy - SEM, X-ray diffraction, infrared spectroscopy and ICP-OES). A kinetic study on non-stationary regime was done to calculate the activation energy by Thermal Gravimetric Analysis evaluating thermochemical and thermocatalytic process of sludge, the latter being in the presence of USY zeolite. As expected, the activation energy evaluated by the mathematical model "Model-free kinetics" applying techniques isoconversionais was lowest for the catalytic tests (57.9 to 108.9 kJ/mol in the range of biomass conversion of 40 to 80%). The pyrolytic plant at a laboratory scale reactor consists of a rotating cylinder whose length is 100 cm with capable of processing up to 1 kg biomass/h. In the process of pyrolysis thermochemical were studied following parameters: temperature of reaction (500 to 600 ° C), flow rate of carrier gas (50 to 200 mL/min), frequency of rotation of centrifugation for condensation of bio-oil (20 to 30 Hz) and flow of biomass (4 and 22 g/min). Products obtained during the process (pyrolytic liquid, coal and gas) were characterized by classical and instrumental analytical techniques. The maximum yield of liquid pyrolytic was approximately 10.5% obtained in the conditions of temperature of 500 °C, centrifugation speed of 20 Hz, an inert gas flow of 200 mL/min and feeding of biomass 22 g/min. The highest yield obtained for the gas phase was 23.3% for the temperature of 600 °C, flow rate of 200 mL/min inert, frequency of rotation of the column of vapor condensation 30 Hz and flow of biomass of 22 g/min. The non-oxygenated aliphatic hydrocarbons were found in greater proportion in the bio-oil (55%) followed by aliphatic oxygenated (27%). The bio-oil had the following characteristics: pH 6.81, density between 1.05 and 1.09 g/mL, viscosity between 2.5 and 3.1 cSt and highest heating value between 16.91 and 17.85 MJ/ kg. The main components in the gas phase were: H2, CO, CO2 and CH4. Hydrogen was the main constituent of the gas mixture, with a yield of about 46.2% for a temperature of 600 ° C. Among the hydrocarbons formed, methane was found in higher yield (16.6%) for the temperature 520 oC. The solid phase obtained showed a high ash content (70%) due to the abundant presence of metals in coal, in particular iron, which was also present in bio-oil with a rate of 0.068% in the test performed at a temperature of 500 oC.

Estudo da circulação hidrodinâmica e da dispersão de óleo na zona costeira entre Macau e Galinhos RN

This paper presents a study on coastal hydrodynamics and the spread of an oil spill in waters off Macau and Galinhos, on the east coast of the state of Rio Grande do Norte in Northeast Brazil. This area has a very marked coastal dynamic owing to the complexity of its geomorphological features, developed in a regime of semidiurnal mesotides involving reefs, spits, estuaries, mangroves, lakes and dunes. The region also plays an important role in the socioeconomic development of the state, given that the production of oil, natural gas, salt and shrimp is concentrated there. The series of oil platforms is interconnected by a pipeline system that carries oil to the local terminal. This pipeline could leak at any moment, causing immense ecological damage. To gauge the risks of an oil leak and resulting contamination of the coastal region, two hydrodynamic scenarios were simulated. The results obtained were used to implement a contaminant transport model with the creation of various oil leak scenarios modeled at different volumes (from small to large) and intensities (sporadic and continuous), at points considered critical for the model (on two platforms and at two pipeline intersections), under different wind (summer and winter) and tidal (high and low at new, full and quarter moon phases) conditions. The use of hydrodynamic circulation computer models as a tool for representing a real project design has been increasingly frequent in recent years, given that they enable the realistic simulation of the hydrodynamic circulation pattern in bodies of water and an analysis of the impacts caused by contaminants released into the water. This study used the computer models contained in SisBAHIA®, in continuous development in the area of Coastal Engineering and Oceanography at COPPE/UFRJ

Extração automatica de feições rodoviáris em imagens digitais

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

Extração semiautomática de contornos de telhado de edifícios com base em snakes e programação dinâmica

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