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

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

Efeito da idade e do repouso pós-colheita de frutos de pepino na semente armazenada

Para avaliar os efeitos da idade e do repouso pós-colheita de frutos de pepino (Cucumis sativus L.) de duas cultivares, Pérola (espinhos escuros) e Rubi (espinhos claros), sobre as alterações na qualidade fisiológica das sementes durante o armazenamento, conduziu-se um experimento em Botucatu, SP e Bandeirantes, PR, durante quatro anos. Os frutos foram colhidos desde os 15 ('Rubi') ou 20 ('Pérola') dias até 45 dias após a antese, permanecendo em repouso pós-colheita por 0, 5, 10 e 15 dias, antes da extração das sementes. Antes e após dois e três anos de armazenamento (sacos de papel em ambiente de laboratório), foram retiradas amostras para avaliação do potencial germinativo e do vigor. Os resultados revelaram que sementes imaturas, retiradas de frutos colhidos precocemente (até 30 dias após a antese) e sem repouso pós-colheita, perderam totalmente a capacidade germinativa no segundo ano de armazenamento. Sementes que apresentavam valores iniciais de germinação mais elevados, as colhidas de frutos maduros (com ou sem repouso pós-colheita) ou de imaturos (30 e 35 dias de idade) com 10 a 15 dias de repouso pós-colheita, mantiveram valores acima de 70% após três anos de armazenamento.

Desenvolvimento de um reator fotoquímico aplicável no tratamento de efluentes fenólicos presentes na indústria do petróleo

With water pollution increment at the last years, so many progresses in researches about treatment of contaminated waters have been developed. In wastewaters containing highly toxic organic compounds, which the biological treatment cannot be applied, the Advanced Oxidation Processes (AOP) is an alternative for degradation of nonbiodegradable and toxic organic substances, because theses processes are generation of hydroxyl radical based on, a highly reactivate substance, with ability to degradate practically all classes of organic compounds. In general, the AOP request use of special ultraviolet (UV) lamps into the reactors. These lamps present a high electric power demand, consisting one of the largest problems for the application of these processes in industrial scale. This work involves the development of a new photochemistry reactor composed of 12 low cost black light fluorescent lamps (SYLVANIA, black light, 40 W) as UV radiation source. The studied process was the photo-Fenton system, a combination of ferrous ions, hydrogen peroxide, and UV radiation, it has been employed for the degradation of a synthetic wastewater containing phenol as pollutant model, one of the main pollutants in the petroleum industry. Preliminary experiments were carrier on to estimate operational conditions of the reactor, besides the effects of the intensity of radiation source and lamp distribution into the reactor. Samples were collected during the experiments and analyzed for determining to dissolved organic carbon (DOC) content, using a TOC analyzer Shimadzu 5000A. The High Performance Liquid Chromatography (HPLC) was also used for identification of the cathecol and hydroquinone formed during the degradation process of the phenol. The actinometry indicated 9,06⋅1018 foton⋅s-1 of photons flow, for 12 actived lamps. A factorial experimental design was elaborated which it was possible to evaluate the influence of the reactants concentration (Fe2+ and H2O2) and to determine the most favorable experimental conditions ([Fe2+] = 1,6 mM and [H2O2] = 150,5 mM). It was verified the increase of ferrous ions concentration is favorable to process until reaching a limit when the increase of ferrous ions presents a negative effect. The H2O2 exhibited a positive effect, however, in high concentrations, reaching a maximum ratio degradation. The mathematical modeling of the process was accomplished using the artificial neural network technique

Degradação fotoquímica de hidrocarbonetos da gasolina em efluentes aquosos

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

Extração do óleo essencial de Cymbopogom winterianus J. com CO2 pressurizado

The extraction with pressurized fluids has become an attractive process for the extraction of essential oils, mainly due the specific characteristics of the fluids near the critical region. This work presents results of the extraction process of the essential oil of Cymbopogon winterianus J. with CO2 under high pressures. The effect of the following variables was evaluated: solvent flow rate (from 0.37 to 1.5 g CO2/min), pressure (66.7 and 75 bar) and temperature (8, 10, 15, 20 and 25 ºC) on the extraction kinetics and the total yield of the process, as well as in the solubility and composition of the C. winterianus essential oil. The experimental apparatus consisted of an extractor of fixed bed and the dynamic method was adopted for the calculation of the oil solubility. Extractions were also accomplished by conventional techniques (steam and organic solvent extraction). The determination and identification of extract composition were done by gas chromatography coupled with a mass spectrometer (GC-MS). The extract composition varied in function of the studied operational conditions and also related to the used extraction method. The main components obtained in the CO2 extraction were elemol, geraniol, citronellol and citronellal. For the steam extraction were the citronellal, citronellol and geraniol and for the organic solvent extraction were the azulene and the hexadecane. The most yield values (2.76%) and oil solubility (2.49x10-2 g oil/ g CO2) were obtained through the CO2 extraction in the operational conditions of T = 10°C, P = 66.7 bar and solvent flow rate 0.85 g CO2/min

Tratamento de materiais contaminados com bifenilas policloradas (PCBS) via extração convencional e fluído supercrítico

The decontamination of the materials has been subject of some studies. One of the factors that it increases the pollution is the lack of responsibility in the discarding of toxic trash, as for example the presence of PCB (Polychlorinated Biphenyls) in the environment. In the Brazilian regulations, the material contaminated with PCB in concentrations higher than 50 ppm must be stored in special places or destroyed, usually by incineration in plasma furnace with dual steps. Due to high cost of the procedure, new methodologies of PCBs removal has been studied. The objective of this study was to develop an experimental methodology and analytical methodology for quantification of removal of PCBs through out the processes of extractions using supercritical fluid and Soxhlet method, also technical efficiency of the two processes of extraction, in the treatment of contaminated materials with PCBs. The materials studied were soils and wood, both were simulated contamination with concentration of 6.000, 33.000 and 60.000 mg of PCB/ kg of materials. Soxhlet extractions were performed using 100 ml of hexane, and temperature of 180 ºC. Extractions by fluid supercritical were performed at conditions of 200 bar, 70°C, and supercritical CO2 flow-rate of 3 g/min for 1-3 hours. The extracts obtained were quantified using Gas chromatography-mass spectrometry (GC/MS). The conventional extractions were made according to factorial experimental planning technique 22, with aim of study the influence of two variables of process extraction for the Soxhlet method: contaminant concentration and extraction time for obtain a maximum removal of PCB in the materials. The extractions for Soxhlet method were efficient for extraction of PCBs in soil and wood in both solvent studied (hexane and ethanol). In the experimental extraction in soils, the better efficient of removal of PCBs using ethanol as solvent was 81.3% than 95% for the extraction using hexane as solvent, for equal time of extraction. The results of the extraction with wood showed statistically it that there is not difference between the extractions in both solvent studied. The supercritical fluid extraction in the conditions studied showed better efficiency in the extraction of PCBs in the wood matrix than in soil, for two hours extractions the obtain percentual of 43.9 ± 0.5 % for the total of PCBs extracted in the soils against 95.1 ± 0,5% for the total of PCBs extracted in the wood. The results demonstrated that the extractions were satisfactory for both technical studied

Estudo da oxidação do metabissulfito de sódio contido no efluente da carcinicultura

The shrimp farming is a process of creation of shrimp that has been growing rapidly in the country, occupying a meaningful space in the Brazilian exporting. In 2003, this activity presented a volume of 60 millions of tons and 220 millions of dollars, being the main generator of employment and income of the primary sector of the northeast economy. However, it is a new activity with c.a. five years in the Rio Grande do Norte State and therefore needs investment in the technological area. Among the wastewaters of this activity, the sulphite solution is being usually applied in the process of fishing, i.e. retrieval of the shrimps from the farming. The aim of this work is to present the oxidation experimental results of the sulphite that may be and to determine what it s the most efficient method, trough laboratory experiments. The measurements were carried out in a mixing reactor inserting air and with hydrogen peroxide addition with and without UV light. The solutions were prepared synthetically with concentrations found in the wastewater of fishing and also collected in locu. The oxidation process using air was monitorated by iodometric analysis for the sulphite and the oxidation using hydrogen peroxide was evaluated with turbidimetric analysis for sulphate, by spectrophotometer. The sulphite was totally oxidized in both processes. The experimental results permit to conclude that the oxidation by hydrogen peroxide is more efficient and allowed to determine the optimum operational conditions in terms of concentration and time of treatment

Degradação foto-fenton de carbono orgânico total em efluentes da indústria de beneficiamento de castanha de caju

At the cashew nut processing industry it is often the generation of wastewaters containing high content of toxic organic compounds. The presence of these compounds is due mainly to the so called liquid of the cashew nut (CNSL). CNSL, as it is commercially known in Brazil, is the liquid of the cashew nut. It looks like an oil with dark brown color, viscous and presents a high toxicity index due to the chemical composition, i.e. phenol compounds, such as anacardic acid, cardol, 2-methyl cardol and monophenol (cardanol). These compounds are bio resistant to the conventional treatments. Furthermore, the corresponding wastewaters present high content of TOC (total organic carbon). Therefore due to the high degree of toxicity it is very important to study and develop treatments of these wastewaters before discharge to the environmental. This research aims to decompose these compounds using advanced oxidative processes (AOP) based on the photo-Fenton system. The advantage of this system is the fast and non-selective oxidation promoted by the hydroxyl radicals (●OH), that is under determined conditions can totally convert the organic pollutants to CO2 and H2O. In order to evaluate the decomposition of the organic charge system samples of the real wastewater od a processing cashew nut industry were taken. This industry was located at the country of the state of Rio Grande do Norte. The experiments were carried out with a photochemical annular reactor equipped with UV (ultra violet) lamp. Based on preliminary experiments, a Doehlert experimental design was defined to optimize the concentrations of H2O2 and Fe(II) with a total of 13 runs. The experimental conditions were set to pH equal to 3 and temperature of 30°C. The power of the lamps applied was 80W, 125W and 250W. To evaluate the decomposition rate measures of the TOC were accomplished during 4 hours of experiment. According to the results, the organic removal obtained in terms of TOC was 80% minimum and 95% maximum. Furthermore, it was gotten a minimum time of 49 minutes for the removal of 30% of the initial TOC. Based on the obtained experimental results, the photo-Fenton system presents a very satisfactory performance as a complementary treatment of the wastewater studied

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitable surfactant was the EO 7 due to the lower reagent onsumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

Determinação experimental e modelagem termodinâmica do ponto de turbidez de sistemas aquosos com tensoativos nonilfenolpolietoxilados

The nonionic surfactants are composed of substances whose molecules in solution, does not ionize. The solubility of these surfactants in water due to the presence of functional groups that have strong affinity for water. When these surfactants are heated is the formation of two liquid phases, evidenced by the phenomenon of turbidity. This study was aimed to determine the experimental temperature and turbidity nonilfenolpoliethoxyled subsequently perform a thermodynamic modeling, considering the models of Flory-Huggins and the empirical solid-liquid equilibrium (SLE). The method used for determining the turbidity point was the visual method (Inoue et al., 2008). The experimental methodology consisted of preparing synthetic solutions of 0,25%, 0,5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12,5%, 15%, 17% and 20% by weight of surfactant. The nonionic surfactants used according to their degree of ethoxylation (9.5, 10, 11, 12 and 13). During the experiments the solutions were homogenized and the bath temperature was gradually increased while the turbidity of the solution temperature was checked visually Inoue et al. (2003). These temperature data of turbidity were used to feed the models evaluated and obtain thermodynamic parameters for systems of surfactants nonilfenolpoliethoxyled. Then the models can be used in phase separation processes, facilitating the extraction of organic solvents, therefore serve as quantitative and qualitative parameters. It was observed that the solidliquid equilibrium model (ESL) was best represented the experimental data.

Estudo da remoção de compostos orgânicos, benzeno e tolueno, em solução aquosa por processo oxidativo avançado do tipo Fenton

The oil and petrochemical industry is responsable to generate a large amount of waste and wastewater. Among some efluents, is possible find the benzene, toluene, ethilbenze and isomers of xilenes compounds, known as BTEX. These compounds are very volatily, toxic for environment and potencially cancerigenous in man. Oxidative advanced processes, OAP, are unconventional waste treatment, wich may be apply on treatment and remotion this compounds. Fenton is a type of OAPs, wich uses the Fenton s reactant, hydrogen peroxide and ferrous salt, to promove the organic degradation. While the Photo-Fenton type uses the Fenton s reactant plus UV radiation (ultraviolet). These two types of OAP, according to literature, may be apply on BTEX complex system. This project consists on the consideration of the utilization of technologies Fenton and Photo-Fenton in aqueous solution in concentration of 100 ppm of BTEX, each, on simulation of condition near of petrochemical effluents. Different reactors were used for each type of OAP. For the analyticals results of amount of remotion were used the SPME technique (solid phase microextraction) for extraction in gaseous phase of these analytes and the gas chromatography/mass espectrometry The arrangement mechanical of Photo-Fenton system has been shown big loss by volatilization of these compounds. The Fenton system has been shown capable of degradate benzene and toluene compounds, with massic percentage of remotion near the 99%.

Determinação de dados de equilíbrio líquido-vapor a altas pressões para sistemas de hidrocarbonetos assimétricos

Crude oil is a complex liquid mixture of organic and inorganic compounds that are dominated by hydrocarbons. It is a mixture of alkanes from the simplest to more complex aromatic compounds that are present derivatives such as gasoline, diesel, alcohol, kerosene, naphtha, etc.. These derivatives are extracted from any oil, however, only with a very high quality, in other words, when the content of hydrocarbons of low molecular weight is high means that production of these compounds is feasible. The American Petroleum Institute (API) developed a classification system for the various types of oil. In Brazil, the quality of most of the oil taken from wells is very low, so it is necessary to generate new technology to develop best practices for refining in order to produce petroleum products of higher commercial value. Therefore, it is necessary to study the thermodynamic equilibrium properties of its derivative compounds of interest. This dissertation aims to determine vapor-liquid equilibrium (VLE) data for the systems Phenilcyclohexane - CO2, and Cyclohexane - Phenilcyclohexane - CO2 at high pressure and temperatures between 30 to 70oC. Furthermore, comparisons between measured VLE experimental data from this work and from the literature in relation to the Peng- Robinson molecular thermodynamic model, using a simulation program SPECS IVCSEP v5.60 and two adjustable interaction parameters, have been performed for modeling and simulation purposes. Finally, the developed apparatus for determination of phase equilibrium data at high pressures is presented

Avaliação do processo oxidativo avançado por permanganato de potássio no tratamento de solos contaminados com idrocarbonetos poliaromáticos

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)

Influência do estresse nutricional programado na composição da microalga isochrysis galbana

Global warming due to Greenhouse Gases (GHG) emissions, especially CO2, has been identified as one of the major problems of the twenty-first century, considering the consequences that could represent to planet. Currently, biological processes have been mentioned as a possible solution, especially CO2 biofixation due to association microalgae growth. This strategy has been emphasized as in addition to CO2 mitigation, occurs the production of biomass rich in compounds of high added value. The Microalgae show high photosynthetic capacity and growth rate higher than the superior plants, doubling its biomass in one day. Its culture does not show seasons, they grow in salt water and do not require irrigation, herbicides or pesticides. The lipid content of these microorganisms, depending on the species, may range from 10 to 70% of its dry weight, reaching 90% under certain culture conditions. Studies indicate that the most effective method to promote increased production of lipids in microalgae is to induce stress by limiting nitrogen content in the culture medium. These evidences justify research continuing the production of biofuels from microalgae. In this paper, it was studied the strategy of increasing the production of lipids in microalgae I. galbana with programmed nutritional stress, due to nitrogen limitation. The physiological responses of microalgae, grown in f / 2 with different concentrations of nitrogen (N: P 15,0-control, N: 5,0 P and N: P 2,5) were monitored. During exponential phase, results showed invariability in the studied conditions. However the cultures subjected to stress in stationary phase, showed lower biomass yields. There was an increase of 32,5% in carbohydrate content and 87.68% in lipids content at N: P ratio of 5,0 and an average decrease of 65% in protein content at N: P ratios of 5, 0 and 2.5. There were no significant variations in ash content, independently of cultivation and growth phase. Despite the limitation of biomass production in cultures with N: P smaller ratios, the increase of lipid accumulation highest lipids yields were observed as compared to the control culture. Given the increased concentration of lipids associated to stress, this study suggests the use of microalgae Isochrysis galbana as an alternative raw material for biofuel production

Estudo da desidratação osmótica da cenoura (Daucus carota) em fatias

In the area of food dehydration, drying of vegetables has a very representative position, it has the objective to preserve the surplus of crops and began with sun drying. Among the vegetable is the carrot, which had its origin in Southeast Asia and in Brazil is a vegetable cultivated enough. The principal objective of this works is to find alternative ways for the conservation of carrot slices by osmotic dehydration with additional drying in heart. Were initially defined the best conditions of pre-osmotic dehydration (temperature, immersion time, type of osmotic solution) based on the results of humidity loss, solid gain, weight reduction and efficiency ratio of predehydrated carrots slices. The osmotic solutions used were composed by NaCl (10%) and sucrose (50 ° Brix) named DO1 and sucrose (50 ° Brix) called DO2. Was made experiment of pre-osmotic dehydration of carrot slices in two temperature levels, with complementary drying in heart with air circulation at 70 º C. Sensory analysis was performed and the study of slices dehydration osmotically and the slices without osmotic treatment. The best results were obtained with the solution DO1 60°C with immersion time of 60 min. The drying of carrot slices presented period of constant rate and decreasing rate. The osmotic pre-treatment reduced the initial humidity of carrot slices, reducing the time to the product to reach the same humidity content. Fick's model, considering the shrinkage, and the Page s model, adapt satisfactorily to experimental datas, allowing the determination of effective diffusion coefficients, consistent with the references. The results of sensory analysis of dry product, showed greater acceptance of sliced carrots with osmotic treatment