144 resultados para Biodegradação de hidrocarbonetos aromáticos
Resumo:
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
Resumo:
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
Resumo:
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
Resumo:
The soil contamination with petroleum is one of the major concern of industries operating in the field and also of environmental agencies. The petroleum consists mainly of alkanes and aromatic hydrocarbons. The most common examples of hydrocarbons polyaromatic are: naphthalene, anthracene, phenanthrene, benzopyrene and their various isomers. These substances cause adverse effects on human and the environment. Thus, the main objective of this work is to study the advanced oxidation process using the oxidant potassium permanganate (KMnO4) for remediation of soils contaminated with two polyaromatic hydrocarbons (PAHs): anthracene and phenanthrene. This study was conducted at bench scale, where the first stage was at batch experiment, using the variables: the time and oxidant dosage in the soil. The second stage was the remediation conducted in continous by a fix column, to this stage, the only variable was remediation time. The concentration of oxidant in this stage was based on the best result obtained in the tests at batch, 2,464 mg / L. The results of degradation these contaminants were satisfactory, at the following dosages and time: (a) 5g of oxidant per kg soil for 48 hours, it was obtained residual contaminants 28 mg phenanthrene and 1.25 mg anthracene per kg of soil and (b) for 7g of oxidant per kg soil in 48 hours remaining 24 mg phenanthrene and anthracene 0.77 mg per kg soil, and therefore below the intervention limit residential and industrial proposed by the State Company of Environmental Sao Paulo (CETESB)
Resumo:
The oil industry, experiencing a great economic and environmental impact, has increasingly invested in researches aiming a more satisfactory treatment of its largest effluent, i.e., produced water. These are mostly discarded at sea, without reuse and after a basic treatment. Such effluent contains a range of organic compounds with high toxicity and are difficult to remove, such as polycyclic aromatic hydrocarbons, salts, heavy metals, etc.. The main objective of this work was to study the solar distillation of produced water pre-treated to remove salts and other contaminants trough of a hybrid system with a pre-heater. This developed apparatus was called solar system, which consists of a solar heater and a conventional distillation solar still. The first device consisted of a water tank, a solar flat plate collector and a thermal reservoir. The solar distillator is of simple effect, with 1m2 of flat area and 20° of inclination. This dissertation was divided in five steps: measurements in the solar system, i.e. temperatures and distillate flow rate and weather data; modeling and simulation of the system; study of vapor-liquid equilibrium of the synthetic wastewater by the aqueous solution of p-xylene; physical and chemical analyses of samples of the feed, distillate and residue, as well as climatology pertinent variables of Natal-RN. The solar system was tested separately, with the supply water, aqueous NaCl and synthetic oil produced water. Temperature measurements were taken every minute of the thermal reservoir, water tank and distillator (liquid and vapor phases). Data of solar radiation and rainfall were obtained from INPE (National Institute for Space Research). The solar pre-heater demonstrated to be effective for the liquid systems tested. The reservoir fluid had an average temperature of 58°C, which enabled the feed to be pre-heated in the distillator. The temperature profile in the solar distillator showed a similar behavior to daily solar radiation, with temperatures near 70°C. The distillation had an average yield of 2.4 L /day, i.e., an efficiency of 27.2%. Mathematical modeling aided the identification of the most important variables and parameters in the solar system. The study of the vapor-liquid equilibrium from Total Organic Carbon (TOC) analysis indicated heteroazeotropia and the vapor phase resulted more concentrated in p-xylene. The physical-chemical analysis of pH, conductivity, Total Dissolved Solids (TDS), chlorides, cations (including heavy metals) and anions, the effluent distillate showed satisfactory results, which presents a potential for reuse. The climatological study indicates the region of Natal-RN as favorable to the operation of solar systems, but the use of auxiliary heating during periods of higher rainfall and cloud cover is also recommended
Resumo:
The composition of petroleum may change from well to well and its resulting characteristics influence significantly the refine products. Therefore, it is important to characterize the oil in order to know its properties and send it adequately for processing. Since petroleum is a multicomponent mixture, the use of synthetic mixtures that are representative of oil fractions provides a better understand of the real mixture behavior. One way for characterization is usually obtained through correlation of physico-chemical properties of easy measurement, such as density, specific gravity, viscosity, and refractive index. In this work new measurements were obtained for density, specific gravity, viscosity, and refractive index of the following binary mixtures: n-heptane + hexadecane, cyclohexane + hexadecane, and benzene + hexadecane. These measurements were accomplished at low pressure and temperatures in the range 288.15 K to 310.95 K. These data were applied in the development of a new method of oil characterization. Furthermore, a series of measurements of density at high pressure and temperature of the binary mixture cyclohexane + n-hexadecane were performed. The ranges of pressure and temperature were 6.895 to 62.053 MPa and 318.15 to 413.15 K, respectively. Based on these experimental data of compressed liquid mixtures, a thermodynamic modeling was proposed using the Peng-Robinson equation of state (EOS). The EOS was modified with scaling of volume and a relatively reduced number of parameters were employed. The results were satisfactory demonstrating accuracy not only for density data, but also for isobaric thermal expansion and isothermal compressibility coefficients. This thesis aims to contribute in a scientific manner to the technological problem of refining heavy fractions of oil. This problem was treated in two steps, i.e., characterization and search of the processes that can produce streams with economical interest, such as solvent extraction at high pressure and temperature. In order to determine phase equilibrium data in these conditions, conceptual projects of two new experimental apparatus were developed. These devices consist of cells of variable volume together with a analytical static device. Therefore, this thesis contributed with the subject of characterization of hydrocarbons mixtures and with development of equilibrium cells operating at high pressure and temperature. These contributions are focused on the technological problem of refining heavy oil fractions
Resumo:
Petroleum Refinery wastewaters (PRW) have hart-to-degrade compounds, such as: phenols, ammonia, cyanides, sulfides, oils and greases and the mono and polynuclear aromatic hydrocarbons: benzene, toluene and xylene (BTX), acenaphthene, nitrobenzene and naphtalene. It is known that the microrganisms activity can be reduced in the presence of certain substances, adversely affecting the biological process of wastewater treatment. This research was instigated due the small number of studies regarding to this specific topic in the avaiable literature. This body of work ims to evaluate the effect of toxic substances on the biodegradability of the organic material found in PRW. Glucose was chosen as the model substrate due to its biodegradable nature. This study was divided into three parts: i) a survey of recalcitants compounds and the removal of phenol by using both biological and photochemical-biological processes; ii) biomass aclimation and iii) evaluation of the inhibitory effect certain compounds have on glucose biodegradation. The phenol degradation experiments were carried out in an activity sludge system and in a photochemical reactor. The results showed the photochemical-biological process to be more effective on phenol degradation, suggesting the superioruty of a combined photochemical-biological treatment when compared with a simple biological process for phenol removal from industry wastewaters. For the acclimation step, was used an activated sludge from industrial wastewaters. A rapid biomass aclimation to a synthetic solution composed of the main inhibitory compouns fpund in a PRW was obtained using the following operation condition: (pH = 7,0; DO ≥ 2,0 mg/L; RS = 20 days e qH = 31,2 and 20,4 hours), The last part was consisted of using respirometry evaluation toxicity effects of selected compounds over oxygen uptake rate to adaptated and non adaptated biomass in the presence of inhibitory compounds. The adaptated sludge showed greater degration capacity, with lower sensibility to toxic effects. The respirometry has proved to be very practical, as the techiniques used were simple and rapid, such as: Chemical Oxygen Demand (COD), Dissolved Oxygen (DO), and Volatile Suspended Solids (VSS). Using the latter it is possible to perform sludge selection to beggingthe process; thus allowing its use for aerobic treatment system`s behacior prediction
Resumo:
The petroleum industry deals with problems which are difficult to solve because of their relation to environmental issues. This is because amounts of residue are generated which vary in type and danger level. The soil contamination by non aqueous liquid phase mixtures, specifically hydrocarbon petroleum has been a reason for great concern, mainly the aromatic and polycyclic aromatic, which present risk to human health due to its carcinogenic and mutagenic character. The Advanced Oxidative Processes (AOP) are efficient technologies for destruction of organic compounds of difficult degradation and, often, they are present in low concentrations. They can be considered clean technologies, because there is no formation of solid by-products or the transfer of pollutor phases. This work focuses on the study of the degradation of petroleum industrial waste, by Advanced Oxidation Processes. Treatments tackling petroleum residues, contaminated soil, and water occurring in the production of petroleum reached the following Polycyclic Aromatic Hydrocarbons (PAH) degradation levels: solid residues 100% in 96 treatment hours; water residue - 100% in 6 treatment hours; soil contamination (COT degradation) - 50.3% in 12 treatment hours. AOP were effective in dealing with petroleum residues thus revealing themselves to be a promising treatment alternative
Resumo:
Increasing concern with the environment, in addition to strict laws, has induced the industries to find altenatives to the treatment of their wastes. Actually, the oil industry has sought solutions to overcome a big environmental problem, i.e., oil field produced water being discharged to the sea. These effluents have organic compounds dissolved, such as polycyclic aromatic hydrocarbons, phenols, benzene, toluene, ethylbenzene and xylenes (BTEX). These compounds are difficult to be removed and have high toxicity. The advanced oxidation processes - AOP are effective to degradation of these organic compounds, because they generate hydroxyl radicals with high potential of oxidation. This work includes the reactor photochemical development applied in the photodegradation treatment (by photo-Fenton process) of wastewaters containing organic compounds dissolved, aiming at treatment and recovery the oil field produced water. The studied reactor allowed the evaluation of two ultraviolet radiation sources that is the main factor to describe the feasibility of the photo¬Fenton treatment, i.e., sun and black light fluorescent lamps, and other relevant variables the process: concentration of reagents, irradiated area and also various reactor configurations to maximize the use of radiation. The organic matter degradation was verified with samples collected during the experimental and analyzed with a total organic carbon analyzer (TOC), which expressed the results in terms of mgC/L. The solar radiation was more effective than radiation from the lamps. it's an important factor for the operation costs cutting. Preliminary experiments applied to oil field produced water treatment have showed satisfactory results, reducing up to 76 % of organic matter
Resumo:
Increasing concern with the environment, in addition to strict laws, has induced the industries to find alternatives to the treatment of their wastes. Actually, the oil industry has sought solutions to overcome a big environmental problem, i.e., oil field produced water being discharged to the sea. These effluents have organic compounds dissolved, such as polycyclic aromatic hydrocarbons, phenols, benzene, toluene, ethylbenzene and xylenes (BTEX). These compounds are difficult to be removed and have high toxicity. The advanced oxidation processes - AOP are effective to degradation of these organic compounds, because they generate hydroxyl radicals with high potential of oxidation. This work includes the reactor photochemical development applied in the photodegradation treatment (by photo-Fenton process) of wastewaters containing organic compounds dissolved, aiming at treatment and recovery the oil field produced water. The studied reactor allowed the evaluation of two ultraviolet radiation sources that is the main factor to describe the feasibility of the photo- Fenton treatment, i.e., sun and black light fluorescent lamps, and other relevant variables the process: concentration of reagents, irradiated area and also various reactor configurations to maximize the use of radiation. The organic matter degradation was verified with samples collected during the experimental and analyzed with a total organic carbon analyzer (TOC), which expressed the results in terms of mgC/L. The solar radiation was more effective than radiation from the lamps. It's an important factor for the operation costs cutting. Preliminary experiments applied to oil field produced water treatment have showed satisfactory results, reducing up to 76 % of organic matter
Resumo:
Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism
Resumo:
In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells
Resumo:
PAHs (Polycyclic Aromatic Hydrocarbons) are a group of organic substances which receive considerable attention because of the carcinogenic and mutagenic properties of some of them. It is therefore important to determine the PAHs in different environmental matrices. Several studies have shown the use of gas chromatography coupled to mass spectrometry as a technique for quantification of PAHs by presenting excellent detection limits. This study aimed to develop an analytical methodology for the determination of 16 PAHs listed by the USEPA, test two methods for extraction of PAHs in water from a 23 factorial design, quantify them through the analytical technique coupled to gas chromatography mass spectrometry (GC/MS) using the method developed, and finally apply the results in chemometrics. The sample was synthesized and subjected to tests of the 23 factorial design, which has the factors: the type of extraction technique (ultrasound and digester), the ratio solvent / sample (1:1 and 1:3) and the type of solvent (dichloromethane / hexane and acetone / dichloromethane). The responses of eight combinations of the factorial design were obtained from the quantification by external calibration in GC/MS. The quantification method was developed from an optimized adaptation of the USEPA Method 8270. We used the full scan mode as a way of acquiring the mass spectra of 16 PAHs. The time in which the samples were subjected to ultrasound was fixed at 10 min and held an investigation to establish the conditions of power and time in the digester. We had the best response in the investigation of the digester power of 100 watts and the time of six minutes. The factorial design of liquid-liquid extraction showed that the most representative factors were: the use of the digester as extraction technique, the ratio solvent / sample 1:1 and the use of a 1:1 mixture of dichloromethane / hexane as a solvent more suitable. These results showed that the 1:1 mixture of dichloromethane / hexane is an excellent mixture to recover the extraction of PAHs an aqueous sample using the microwave digester. The optimization of the method of separation, identification and quantification of PAHs in the GC/MS was valid for 16 PAHs present in each chromatogram of the samples
Resumo:
Polycyclic aromatic hydrocarbons (PAHs) constitute a family of compounds characterized by having two or more condensed aromatic rings and for being a class of substances that are widely distributed in the environment as a complex mixture, being very persistent in the environment due to its low solubility in water. The application of chemometric methods to analytical chemistry has provided excellent results in studying the solubility of PAHs in aqueous media in order to understand the mechanisms involved in environmental contamination. The method consists in analyzing the solubilization of PAHs from diesel oil in water varying parameters such as stirring time, volume of oil added and pH, using a full factorial design of two levels and three factors. PAHs were extracted with n-hexane and analyzed by fluorescence spectroscopy because they have molecular characteristics fluorescent due to the large number of condensed rings and links, and gas chromatography coupled to a mass spectrometer (GC-MS). The results of fluorescence analysis showed that only the stirring time and pH influenced the solubility of PAHs in diesel fuel. How is a non-selective technique for the study of fluorescence was performed on form and semi-quantitative. And for the chromatographic analysis the results showed that the solubility of the different PAHs is influenced differently so that you can classify them into groups by the results of the effects
Resumo:
The synthesis of MFI-type zeolite membranes was carried by the process in situ or hydrothermal crystallization. We studied the homogenization time of the room temperature and gel filtration just before the crystallization step performed out in an oven, thus obtaining a more uniform zeolite film. The powder synthesized zeolite (structure type MFI, Silicalite) was characterized by several complementary techniques such as Xray diffraction (XRD), scanning electron microscopy (SEM), thermal analysis, temperature programmed desorption (TPD), Fourier Transform infrared spectroscopy (FTIR) and textural analysis by nitrogen adsorption (specific surface area). For the purpose of evaluating the quality of the layer supported on the ceramic support, N2 permeation tests were carried starting from room temperature to 600 °C, where values were observed values more appropriate permeation from 200 °C. With the data obtained, it was made into a graph of temperature versus permeation function, the curve of surface diffusion was found. For scanning electron microscopy, we observed the formation of homogeneous crystals and the zeolite film showed no fissures or cracks, indicating that the process of synthesis and subsequent treatments not damaged the zeolite layer on the support. Carried permeation studies were found values ranging from 3.64x10-6 to 3.78x10-6, 4.71x10-6 to 5.02x10-6, to pressures 20 and 25 psi, respectively. And the mixture xylenes/N2 values were between 5.39x10-6 to 5.67x10-6 and 8.13x10-6 to 8.36x10-6, also for pressures of 20 and 25 psi. The values found for the separation factor were 15.22 at 400 °C in the first experiment and 1.64 for the second experiment at a temperature of 150 °C. It is concluded that the Silicalite membrane was successfully synthesized and that it is effective in the separation of binary mixtures of xylenes