Concentrating solar power + desalination plants (CSP+D): models and performance analysis

Tese submetida à Universidade de Lisboa, Instituto Superior Técnico e aprovada em provas públicas para a obtenção do Grau de Doutor em Sistemas Sustentáveis de Energia.

Análise do circuito de água de refrigeração de uma unidade de regeneração de solventes

A EGEO Solventes S.A. é uma empresa com atividade na área da gestão de resíduos, focando-se na regeneração de solventes. Na unidade industrial da empresa recorre-se à destilação de misturas de solventes usados para obtenção do solvente regenerado. Esta operação exige água para o arrefecimento e condensação dos destilados das misturas de solventes, que, posteriormente, é arrefecida em torres de refrigeração instaladas na unidade. Durante o tempo de operação da unidade foram identificados problemas na condensação dos solventes limpos, obrigando a que se ligassem dois condensadores em série para assegurar a condensação do vapor produzido na destilação e à necessidade de caudais maiores de utilidade fria. Outro dos problemas identificados foi a baixa eficiência das torres de refrigeração, uma vez que a diferença de temperaturas da água à entrada e à saída do equipamento é muito baixa. Assim sendo, o objetivo principal deste trabalho é identificar as principais causas para a baixa eficiência dos equipamentos e propor alterações aos equipamentos ou soluções de melhoria do processo. Para diagnosticar estes problemas foram recolhidas amostras para determinação da composição do solvente limpo obtido e registadas as condições de operação para obtenção da mistura ECOSOLVE MET. Recorrendo a metodologias de projeto determinou-se o fator de resistência do fouling no condensador C1 e seguidamente a geometria, a alocação de correntes e a orientação do condensador mais adequadas e concluiu-se que este está sujeito a uma forte acumulação de material nas paredes e que a melhor opção seria recorrer a um permutador horizontal com condensação na carcaça, mas aumentando o número de passagens da água nos tubos. No que diz respeito à operação da torre de arrefecimento, determinou-se o caudal mínimo de ar para determinadas condições de operação e verificou-se que o caudal de ar alimentado à torre era superior ao mínimo determinado. Foram observadas diferenças quando comparadas as condições de operação experimentais com a performance da unidade usando oito enchimentos estruturados e aleatórios para os quais há dados na literatura São também apresentadas alternativas de operação e o projeto de uma torre de arrefecimento de água, sustentada numa análise económica de todo o processo. As simulações foram realizadas com recurso ao AspenPlus®.

Análisis de la estática para la síntesis de furfural por destilación reactiva

Hoy día, se presta la atención a los derivados de furano y a los procesos catalíticos alrededor de éstos para la conversión de los azúcares contenidos en la biomasa lignocelulósica. En este sentido, el furfural también recibe una especial atención como potencial químico para la producción de bioproductos y biocombustibles. Debido a las dificultades presentadas en la separación del furfural en el proceso convencional, en este trabajo se presenta el análisis de la separación para obtener furfural de alta pureza a partir de xilosa deshidratada por destilación reactiva como proceso no convencional, aplicando la teoría básica de análisis estático para obtener la mejor información del proceso de destilación reactiva, obteniendo un esquema tecnológico que permite alcanzar una fracción molar de furfural de aproximadamente 0.9.

Direct catalytic macrolactonization and application of the phase separation strategy in complex molecule synthesis

Les macrolactones sont des squelettes structuraux importants dans de nombreuses sphères de l’industrie chimique, en particulier dans les marchés pharmaceutiques et cosmétiques. Toutefois, la stratégie traditionnelle pour la préparation de macrolactones demeure incommode en requérant notamment l’ajout (super)stœchiométrique d’agents activateurs. Conséquemment, des quantités stœchiométriques de sous-produits sont générées; ils sont souvent toxiques, dommageables pour l’environnement et nécessitent des méthodes de purification fastidieuses afin de les éliminer. La présente thèse décrit le développement d’une macrolactonisation efficace catalysée au hafnium directement à partir de précurseurs portant un acide carboxylique et un alcool primaire, ne générant que de l’eau comme sous-produit et ne nécessitant pas de techniques d’addition lente et/ou azéotropique. Le protocole a également été adapté à la synthèse directe de macrodiolides à partir de mélanges équimolaires de diols et de diacides carboxyliques et à la synthèse de dimères tête-à-queue de seco acides. Des muscs macrocycliques ainsi que des macrolactones pertinentes à la chimie médicinale ont pu être synthétisés avec l’approche développée. Un protocole pour l’estérification directe catalysée au hafnium entre des acides carboxyliques et des alcools primaires a aussi été développé. Différentes méthodes pour la macrolactonisation catalytique directe entre des alcools secondaires et des acides carboxyliques ont été étudiées. En outre, la stratégie de séparation de phase en macrocyclisation en débit continu a été appliquée lors de la synthèse totale formelle de la macrolactone ivorenolide A. Les étapes-clés de la synthèse incluent une macrocyclisation par le couplage d’alcynes de Glaser-Hay et une réaction de métathèse d’alcènes Z-sélective.

Vapor–liquid equilibrium of binary mixtures containing isopropyl acetate and alkanols at 101.32 kPa

Isobaric vapor-liquid equilibria of binary mixtures of isopropyl acetate plus an alkanol (1-propanol, 2-propanol, 1-butanol, or 2-butanol) were measured at 101.32 kPa, using a dynamic recirculating still. An azeotropic behavior was observed only in the mixtures of isopropyl acetate + 2-propanol and isopropyl acetate + 1-propanol. The application of four thermodynamic consistency tests (the Herington test, the Van Ness test, the infinite dilution test, and the pure component test) showed the high quality of the experimental data. Finally, both NRTL and UNIQUAC activity coefficient models were successfully applied in the correlation of the measured data, with the average absolute deviations in vapor phase composition and temperature of 0.01 and 0.16 K, respectively.

Selection of optimal operating conditions based on minimum energy consumption for an acrylonitrile recovery unit

The selection of the optimal operating conditions for an industrial acrylonitrile recovery unit was conducted by the systematic application of the response surface methodology, based on the minimum energy consumption and products specifications as process constraints. Unit models and plant simulation were validated against operating data and information. A sensitivity analysis was carried out in order to identify the set of parameters that strongly affect the trajectories of the system while keeping products specifications. The results suggest that energy savings of up to 10% are possible by systematically adjusting operating conditions.

Antimicrobial activity of the essential oils of Dittrichia viscosa subsp viscosa on Helicobacter pylori

Dittrichia viscosa subsp. viscosa (Compositae) is found on edges, wood clearings and in waste places of the Iberian Peninsula. Aerial parts of D. viscosa were collected at flowering phase in September-October 2001 around Lisbon, Portugal and the essential oils isolated by hydro-distillation for 4 h using a Clevenger-type apparatus. The oils were analyzed by gas chromatography and gas chromatography-mass spectrometry. Preliminary examination of the essential oils allowed the identification of 32 components. Only four components reached percentages over 5%: fokienol (11.8%), T-muurorol (7.9%), (E)-nerolidol (5.5%) and delta-cadinene (5.0%). The essential oils were tested against Helicobacterpylori and Listeria monocytogenes. Essential oils did not have antimicrobial activity against L. monocytogenes. The essential oil at 0.88 to 22.22 mu g.ml(-1) did not inhibit the growth of H. pylori, affected the growth slightly at 44.40 mu g.ml(-1), and completely inhibited the growth at 88.80 to 133.20 mu g.ml(-1) Results show that use of D. viscosa essential oil in the treatment of gastric disorders caused by H. pylori can be effective.

Aplicação de termogravimetria acoplada à espectrometria de massas para caracterização de petróleo e determinação da curva de evolução de gás sulfídrico

With the new discoveries of oil and gas, the exploration of fields in various geological basins, imports of other oils and the development of alternative fuels, more and more research labs have evaluated and characterized new types of petroleum and derivatives. Therefore the investment in new techniques and equipment in the samples analysis to determine their physical and chemical properties, their composition, possible contaminants, especification of products, among others, have multiplied in last years, so development of techniques for rapid and efficient characterization is extremely important for a better economic recovery of oil. Based on this context, this work has two main objectives. The first one is to characterize the oil by thermogravimetry coupled with mass spectrometry (TG-MS), and correlate these results with from other types of characterizations data previously informed. The second is to use the technique to develop a methodology to obtain the curve of evaluation of hydrogen sulfide gas in oil. Thus, four samples were analyzed by TG-MS, and X-ray fluorescence spectrometry (XRF). TG results can be used to indicate the nature of oil, its tendency in coke formation, temperatures of distillation and cracking, and other features. It was observed in MS evaluations the behavior of oil main compounds with temperature, the points where the volatilized certain fractions and the evaluation gas analysis of sulfide hydrogen that is compared with the evaluation curve obtained by Petrobras with another methodology

Determination of borneol and other chemical compounds of essential oil of Dryobalanops aromatica exudate from Malaysia

Purpose: To determine borneol and other chemical compounds of essential oil derived from the exudate of Dryobalanops aromatica aromatica in Malaysia. Methods: Exudate was collected from D. aromatica and subjected to fractional distillation to obtain essential oil. Gas chromatography-mass spectrometry (GC-MS) was performed to characterize the composition of the isolated essential oil. Results: Essential oil (7.58 %) was obtained with the highest yield (3.24 %) in the first 2 h of fractional distillation. Thirty compounds which accounted for 97.56 % of total essential oil composition were identified by GC-MS, and they include sesquiterpenes (46.87 %), monoterpenes (31.05 %), oxygenated monoterpenes (16.76 %) and oxygenated sesquiterpenes (2.13 %). Borneol (0.74 %) was also detected in the essential oil. Conclusion: Borneol and other terpenoid compounds are present in the essential oil of the exudate of D. aromatica

Antimicrobial activity of the essential oils of Dittrichia viscosa subsp viscosa on Helicobacter pylori

Dittrichia viscosa subsp. viscosa (Compositae) is found on edges, wood clearings and in waste places of the Iberian Peninsula. Aerial parts of D. viscosa were collected at flowering phase in September-October 2001 around Lisbon, Portugal and the essential oils isolated by hydro-distillation for 4 h using a Clevenger-type apparatus. The oils were analyzed by gas chromatography and gas chromatography-mass spectrometry. Preliminary examination of the essential oils allowed the identification of 32 components. Only four components reached percentages over 5%: fokienol (11.8%), T-muurorol (7.9%), (E)-nerolidol (5.5%) and delta-cadinene (5.0%). The essential oils were tested against Helicobacterpylori and Listeria monocytogenes. Essential oils did not have antimicrobial activity against L. monocytogenes. The essential oil at 0.88 to 22.22 mu g.ml(-1) did not inhibit the growth of H. pylori, affected the growth slightly at 44.40 mu g.ml(-1), and completely inhibited the growth at 88.80 to 133.20 mu g.ml(-1) Results show that use of D. viscosa essential oil in the treatment of gastric disorders caused by H. pylori can be effective.

Disfarce de intenções : exposição e ocultação em Jac Leirner

Dissertação (mestrado)—Universidade de Brasília, Instituto de Artes, Programa de Pós-Graduação em Arte, 2016.

Pirólise térmica e catalítica de resíduos de vácuo gerados no refino de petróleo

In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

Estudo de modelos composicionais de óleo na injeção contínua de vapor

The objective of the thermal recovery is to heat the resevoir and the oil in it to increase its recovery. In the Potiguar river basin there are located several heavy oil reservoirs whose primary recovery energy provides us with a little oil flow, which makes these reservoirs great candidates for application of a method of recovery advanced of the oil, especially the thermal. The steam injection can occur on a cyclical or continuous manner. The continuous steam injection occurs through injection wells, which in its vicinity form a zone of steam that expands itself, having as a consequence the displace of the oil with viscosity and mobility improved towards the producing wells. Another possible mechanism of displacement of oil in reservoirs subjected to continuous injection of steam is the distillation of oil by steam, which at high temperatures; their lighter fractions can be vaporized by changing the composition of the oil produced, of the oil residual or to shatter in the amount of oil produced. In this context, this paper aims to study the influence of compositional models in the continuous injection of steam through in the analysis of some parameters such as flow injection steam and temperature of injection. Were made various leading comparative analysis taking the various models of fluid, varying from a good elementary, with 03 pseudocomponents to a modeling of fluids with increasing numbers of pseudocomponents. A commercial numerical simulator was used for the study from a homogeneous reservoir model with similar features to those found in northeastern Brazil. Some conclusions as the increasing of the simulation time with increasing number of pseudocomponents, the significant influence of flow injection on cumulative production of oil and little influence of the number of pseudocomponents in the flows and cumulative production of oil were found

Avaliação térmica dos resíduos da destilação atmosférica das blendas - biodiesel/diesel

The worldwide concern regarding the use of sustainable energy and preserving the environment are determining factors in the search for resources and alternative sources of energy and therefore fuel less aggressive nature. In response to these difficulties Biodiesel has emerged as a good solution because it is produced from renewable sources, produces burns cleaner and is easily reproducible. This work was synthesized with biodiesel oil, sunflower via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the blends BX (a proportion of biodiesel X = 5, 10, 15 and 20 %). Atmospheric distillation of the analysis, performed in blends with and without BHT were collected residue generated by each sample and performed a study heat from the thermogravimetric analysis at a heating rate of 10 °C*min-1, nitrogen atmosphere and heating to 600 °C. According to the specifications of Resolution N 7/2008 for biodiesel, it was found that the synthesized material was in accordance with the specifications. For blends showed that the samples are in accordance with the Resolution of ANP N 42/2009. From the TG / DTG curves of the samples of biodiesel, blends and waste can be seen that these show a single loss of thermal decomposition concerning constituents present in each sample. The blends without BHT with ratios of 5%, 10% and 15% biodiesel showed a lower amount of waste (1,07%; 1,09% e 1,10%) to mineral diesel (1,15%). Therefore, it is concluded that the addition of biodiesel with diesel mineral can improve some physico-chemical parameters, but also, depending on the added amount, decreasing the amount of waste generated. This fact is of great importance because the carbonaceous residue can cause problems in mechanical equipment and parts for vehicles, causing more frequent maintenance, and this is not desirable

Estudo térmico dos resíduos gerados da destilação atmosférica das misturas diesel/biodiesel de dendê

The growing world demand for energy supplied by fossil fuels, a major contributor to the emission of pollutants into the atmosphere and causing environmental problems, has been encouraging governments and international organizations to reflect and encourage the use of alternative renewable sources. Among these new possibilities deserves attention biodiesel, fuel cleaner and easy to reproduce. The study of new technologies involving that source is necessary. From this context, the paper aims at analyzing the thermal stability by thermogravimetric analysis, of the waste generated from atmospheric distillation of mixtures with ratios of 5, 10, 15 and 20% palm biodiesel in diesel with and without addition of BHT antioxidant. It was synthesized biodiesel through palm oil, via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the diesel common indoor type (S1800) from a gas station BR. The diesel was already added with 5% biodiesel, and thus the proportions used for these blends were subtracted from the existing ratio in diesel fuel, resulting in the following proportions palm oil biodiesel: 0% (B5), 5% (B10), 10 % (B15) and 15% (B20). From atmospheric distillation analysis, performed in mixtures with and without BHT were collected residue generated by each sample and performed a thermal study from the thermogravimetric analysis at a heating rate of 10 °C.min-1, nitrogen atmosphere and heating to 600 ° C. According to the specifications of Resolution No. 7/2008 for biodiesel, it was found that the material was synthesized in accordance with the specifications. For mixtures, it was noted that the samples were in accordance with the ANP Resolution No. 42/2009. Given the TG / DTG curves of the samples of waste mixtures with and without BHT antioxidant was able to observe that they showed a single stage of thermal decomposition attributed to decomposition of heavy hydrocarbons and esters and other heavier constituents of the waste sample weighed. The thermal behavior of residues from atmospheric distillation of mixtures of diesel / biodiesel is very important to understand how this affects the proper functioning of the engine. A large amount of waste can generate a high content of particulate material, coke formation and carbonaceous deposits in engine valves, compromising their performance