981 resultados para Fluid-solid Reactions
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Sub-nanosecond bipolar high voltage pulses are a very important tool for food processing, medical treatment, waste water and exhaust gas processing. A Hybrid Modulator for sub-microsecond bipolar pulse generation, comprising an unipolar solid-state Marx generator connected to a load through a stack Blumlein system that produces bipolar pulses and further multiplies the pulse voltage amplitude, is presented. Experimental results from an assembled prototype show the generation of 1000 V amplitude bipolar pulses with 100 ns of pulse width and 1 kHz repetition rate.
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This paper, reports experimental work on the use of new heterogeneous solid basic catalysts for biodiesel production: double oxides of Mg and Al, produced by calcination, at high temperature, of MgAl lamellar structures, the hydrotalcites (HT). The most suitable catalyst system studied are hydrotalcite Mg:Al 2:1 calcinated at 507 degrees C and 700 degrees C, leading to higher values of FAME also in the second reaction stage. One of the prepared catalysts resulted in 97.1% Fatty acids methyl esters (FAME) in the 1st reaction step, 92.2% FAME in the 2nd reaction step and 34% FAME in the 3rd reaction step. The biodiesel obtained in the transesterification reaction showed composition and quality parameters within the limits specified by the European Standard EN 14214. 2.5% wt catalyst/oil and a molar ratio methanol:oil of 9:1 or 12:1 at 60 -65 degrees C and 4 h of reaction time are the best operating conditions achieved in this study. This study showed the potential of Mg/Al hydrotalcites as heterogeneous catalysts for biodiesel production. (C) 2011 Elsevier Ltd. All rights reserved.
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The new hexanuclear mixed-valence vanadium complex [V3O3(OEt)(ashz)(2)(mu-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.
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In this contribution, we investigate the low-temperature, low-density behaviour of dipolar hard-sphere (DHS) particles, i.e., hard spheres with dipoles embedded in their centre. We aim at describing the DHS fluid in terms of a network of chains and rings (the fundamental clusters) held together by branching points (defects) of different nature. We first introduce a systematic way of classifying inter-cluster connections according to their topology, and then employ this classification to analyse the geometric and thermodynamic properties of each class of defects, as extracted from state-of-the-art equilibrium Monte Carlo simulations. By computing the average density and energetic cost of each defect class, we find that the relevant contribution to inter-cluster interactions is indeed provided by (rare) three-way junctions and by four-way junctions arising from parallel or anti-parallel locally linear aggregates. All other (numerous) defects are either intra-cluster or associated to low cluster-cluster interaction energies, suggesting that these defects do not play a significant part in the thermodynamic description of the self-assembly processes of dipolar hard spheres. (C) 2013 AIP Publishing LLC.
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A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R2) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD < 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposedmaximumresidue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.
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Mestrado em Engenharia Química. Ramo Tecnologias de Protecção Ambiental.
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Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química
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O objectivo desta tese é dimensionar um secador em leito fluidizado para secagem de cereais, nomeadamente, secagem de sementes de trigo. Inicialmente determinaram-se as condições de hidrodinâmica (velocidade de fluidização, TDH, condições mínimas de “slugging”, expansão do leito, dimensionamento do distribuidor e queda de pressão). Com as condições de hidrodinâmica definidas, foi possível estimar as dimensões físicas do secador. Neste ponto, foram realizados estudos relativamente à cinética da secagem e à própria secagem. Foi também estudado o transporte pneumático das sementes. Deste modo, determinaram-se as velocidades necessárias ao transporte pneumático e respectivas quedas de pressão. Por fim, foi realizada uma análise custos para que se soubesse o custo deste sistema de secagem. O estudo da secagem foi feito para uma temperatura de operação de 50ºC, tendo a ressalva que no limite se poderia trabalhar com 60ºC. A velocidade de operação é de 2,43 m/s, a altura do leito fixo é de 0,4 m, a qual sofre uma expansão durante a fluidização, assumindo o valor de 0,79 m. O valor do TDH obtido foi de 1,97 m, que somado à expansão do leito permite obter uma altura total da coluna de 2,76 m. A altura do leito fixo permite retirar o valor do diâmetro que é de 0,52 m. Verifica-se que a altura do leito expandido é inferior à altura mínima de “slugging” (1,20 m), no entanto, a velocidade de operação é superior à velocidade mínima de “slugging” (1,13 m/s). Como só uma das condições mínimas é cumprida, existe a possibilidade da ocorrência de “slugging”. Finalmente, foi necessário dimensionar o distribuidor, que com o diâmetro de orifício de 3 mm, valor inferior ao da partícula (3,48 mm), permite a distruibuição do fluido de secagem na coluna através dos seus 3061 orifícios. O inicio do estudo da secagem centrou-se na determinação do tempo de secagem. Além das duas temperaturas atrás referidas, foram igualmente consideradas duas humidades iniciais para os cereais (21,33% e 18,91%). Temperaturas superiores traduzem-se em tempos de secagem inferiores, paralelamente, teores de humidade inicial inferiores indicam tempos menores. Para a temperatura de 50ºC, os tempos de secagem assumiram os valores de 2,8 horas para a 21,33% de humidade e 2,7 horas para 18,91% de humidade. Foram também tidas em conta três alturas do ano para a captação do ar de secagem, Verão e Inverno representando os extremos, e a Meia- Estação. Para estes três casos, foi possível verificar que a humidade específica do ar não apresenta alterações significativas entre a entrada no secador e a corrente de saída do mesmo equipamento, do mesmo modo que a temperatura de saída pouco difere da de entrada. Este desvio de cerca de 1% para as humidades e para as temperaturas é explicado pela ausência de humidade externa nas sementes e na pouca quantidade de humidade interna. Desta forma, estes desvios de 1% permitem a utilização de uma razão de reciclagem na ordem dos 100% sem que o comportamento da secagem se altere significativamente. O uso de 100% de reciclagem permite uma poupança energética de cerca de 98% no Inverno e na Meia-Estação e de cerca de 93% no Verão. Caso não fosse realizada reciclagem, seria necessário fornecer à corrente de ar cerca de 18,81 kW para elevar a sua temperatura de 20ºC para 50ºC (Meia-Estação), cerca de 24,67 kW para elevar a sua temperatura de 10ºC para 50ºC (Inverno) e na ordem dos 8,90 kW para elevar a sua temperatura dos 35ºC para 50ºC (Verão). No caso do transporte pneumático, existem duas linhas, uma horizontal e uma vertical, logo foi necessário estimar o valor da velocidade das partículas para estes dois casos. Na linha vertical, a velocidade da partícula é cerca de 25,03 m/s e cerca de 35,95 m/s na linha horizontal. O menor valor para a linha vertical prende-se com o facto de nesta zona ter que se vencer a força gravítica. Em ambos os circuitos a velocidade do fluido é cerca de 47,17 m/s. No interior da coluna, a velocidade do fluido tem o valor de 10,90 m/s e a velocidade das partículas é de 1,04 m/s. A queda de pressão total no sistema é cerca de 2408 Pa. A análise de custos ao sistema de secagem indicou que este sistema irá acarretar um custo total (fabrico mais transporte) de cerca de 153035€. Este sistema necessita de electricidade para funcionar, e esta irá acarretar um custo anual de cerca de 7951,4€. Embora este sistema de secagem apresente a possibilidade de se realizar uma razão de reciclagem na ordem dos 100% e também seja possível adaptar o mesmo para diferentes tipos de cereais, e até outros tipos de materiais, desde que possam ser fluidizados, o seu custo impede que a realização deste investimento não seja atractiva, especialmente tendo em consideração que se trata de uma instalação à escala piloto com uma capacidade de 45 kgs.
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Master Thesis in Mechanical Engineering field of Maintenance and Production
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We consider a fluid of hard boomerangs, each composed of two hard spherocylinders joined at their ends at an angle Psi. The resulting particle is nonconvex and biaxial. The occurence of nematic order in such a system has been investigated using Straley's theory, which is a simplificaton of Onsager's second-virial treatment of long hard rods, and by bifurcation analysis. The excluded volume of two hard boomerangs has been approximated by the sum of excluded volumes of pairs of constituent spherocylinders, and the angle-dependent second-virial coefficient has been replaced by a low-order interpolating function. At the so-called Landau point, Psi(Landau)approximate to 107.4 degrees, the fluid undergoes a continuous transition from the isotropic to a biaxial nematic (B) phase. For Psi not equal Psi(Landau) ordering is via a first-order transition into a rod-like uniaxial nematic phase (N(+)) if Psi > Psi(Landau), or a plate-like uniaxial nematic (N(-)) phase if Psi < Psi(Landau). The B phase is separated from the N(+) and N(-) phases by two lines of continuous transitions meeting at the Landau point. This topology of the phase diagram is in agreement with previous studies of spheroplatelets and biaxial ellipsoids. We have checked the accuracy of our theory by performing numerical calculations of the angle-dependent second virial coefficient, which yields Psi(Landau)approximate to 110 degrees for very long rods, and Psi(Landau)approximate to 90 degrees for short rods. In the latter case, the I-N transitions occur at unphysically high packing fractions, reflecting the inappropriateness of the second-virial approximation in this limit.
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The authors extend their earlier work on the stability of a reacting binary polymer blend with respect to demixing [D. J. Read, Macromolecules 31, 899 (1998); P. I. C. Teixeira , Macromolecules 33, 387 (2000)] to the case where one of the polymers is rod-like and may order nematically. As before, the authors combine the random phase approximation for the free energy with a Markov chain model for the chemistry to obtain the spinodal as a function of the relevant degrees of reaction. These are then calculated by assuming a simple second-order chemical kinetics. Results are presented, for linear systems, which illustrate the effects of varying the proportion of coils and rods, their relative sizes, and the strength of the nematic interaction between the rods. (c) 2007 American Institute of Physics.
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A new procedure for determining eleven organochlorine pesticides in soils using microwave-assisted extraction (MAE) and headspace solid phase microextraction (HS-SPME) is described. The studied pesticides consisted of mirex, α- and γ-chlordane, p,p’-DDT, heptachlor, heptachlor epoxide isomer A, γ-hexachlorocyclohexane, dieldrin, endrin, aldrine and hexachlorobenzene. The HS-SPME was optimized for the most important parameters such as extraction time, sample volume and temperature. The present analytical procedure requires a reduced volume of organic solvents and avoids the need for extract clean-up steps. For optimized conditions the limits of detection for the method ranged from 0.02 to 3.6 ng/g, intermediate precision ranged from 14 to 36% (as CV%), and the recovery from 8 up to 51%. The proposed methodology can be used in the rapid screening of soil for the presence of the selected pesticides, and was applied to landfill soil samples.
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A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1–14.3 lg/L and 0.2–43.3 lg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R2) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed.
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The present work describes a solid-phase microextraction (SPME) gas chromatography_tandem mass spectrometry (MS/MS) method to quantify 24 pesticides in fortified white wine and fortified red wine. In this study “fortified wine” refers to a wine in which fermentation is arrested before completion by alcohol distillate addition, allowing sugar and alcoholic contents to be higher (around 80-100 g/L total sugars and 19-22% alcohol strength (v/v)). The analytical method showed good linearity, presenting correlation coefficients (R2) ≥ 0.989 for all compounds. Limits of detection (LOD) and quantitation (LOQ) in the ranges of 0.05-72.35 and 0.16-219.23 μg/L, respectively, were obtained. LOQs are below the maximum residue levels (MRL) set by European Regulation for grapes. The proposed method was applied to 17 commercial fortified wines. The analyzed pesticides were not detected in the wines tested.
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In order to combat a variety of pests, pesticides are widely used in fruits. Several extraction procedures (liquid extraction, single drop microextraction, microwave-assisted extraction, pressurized liquid extraction, supercritical fluid extraction, solid-phase extraction, solid-phase microextraction, matrix solid-phase dispersion, and stir bar sorptive extraction) have been reported to determine pesticide residues in fruits and fruit juices. The significant change in recent years is the introduction of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods in these matrices analysis. A combination of techniques reported the use of new extraction methods and chromatography to provide better quantitative recoveries at low levels. The use of mass spectrometric detectors in combination with liquid and gas chromatography has played a vital role to solve many problems related to food safety. The main attention in this review is on the achievements that have been possible because of the progress in extraction methods and the latest advances and novelties in mass spectrometry, and how these progresses have influenced the best control of food, allowing for an increase in the food safety and quality standards.