Flow phenomena, heat and mass transfer in microchannel reactors

The studies of flow phenomena, heat and mass transfer in microchannel reactors are beneficial to estimate and evaluate the ability of microchannel reactors to be operated for a given process reaction such as Fischer-Tropsch synthesis. The flow phenomena, for example, the flow regimes and flow patterns in microchannel reactors for both single phase and multiphase flow are affected by the configuration of the flow channel. The reviews of the previous works about the analysis of related parameters that affect the flow phenomena are shown in this report. In order to predict the phenomena of Fischer-Tropsch synthesis in microchannel reactors, the 3-dimensional computational fluid dynamic simulation with commercial software package FLUENT was done to study the flow phenomena and heat transfer for gas phase Fischer-Tropsch products flow in rectangular microchannel with hydraulic diameter 500 ¿m and length 15 cm. Numerical solution with slip boundary condition was used in the simulation and the flowphenomena and heat transfer were determined.

Typpeä sisältävien jätevesien käsittely 2-n-PRO menetelmällä

Työssä tutkittiin kaksivaiheisen typenpoistoprosessin (2-N-PRO) soveltuvuutta Joutsenon Kukkuroinmäen aluejätekeskuksen kompostointilaitoksen jätevesille pilot-kokein 12.1.- 5.4.2006. Kompostilaitoksella on jätevesien esikäsittelytarve korkeista ammoniumtyppipitoisuuksista johtuen. Pilot-laitteisto koostuu sekoitussäiliöstä, strippaustornista ja katalyyttipolttimesta. Käsiteltävän jäteveden pH nostetaan korkealle tasolle, jolloin ammoniumtyppi muuttuu ammoniakiksi. Vesi johdetaan strippaustorniin, jossa se sadetetaan tornin pohjalle. Ammoniakki erottuu sadetuksessa ilmaan, joka imetään katalyyttipolttimelle. Katalyyttinen poltin käsittelee ammoniakkia typpikaasuksi. Pilot-kokeet suoritettiin jatkuvatoimisesti. Laitteisto pystyy erottamaan jätevedestä ammoniumtyppeä ammoniakiksi ja käsittelemään ammoniakin pääosin typpikaasuksi. Lisäksi suoritettiin panoskoe, jonka tulokset tukevat jatkuvatoimisesta käytöstä saatuja tuloksia.

Development of a PC Tool for Estimating Pressure Drops in Forced-convection Boiler Tubes

Kaksifaasivirtauksen kuvaamiseen käytettävät mallit, ja menetelmät kaksifaasivirtauksen painehäviön määrittämiseksi kehittyvät yhä monimutkaisimmiksi. Höyrystinputkissa tapahtuvien painehäviöiden arvioinnin vaatiman laskennan suorittamiseksi tietokoneohjelman kehittäminen on välttämätöntä. Tässä työssä on kehitetty itsenäinen PC-ohjelma painehäviöiden arvioimiseksi pakotetulle konvektiovirtaukselle pystysuorissa höyrykattilan höyrystinputkissa. Veden ja vesihöyryn aineominaisuuksien laskentaan käytetään IAPWS-IF97 –yhtälökokoelmaa sekä muita tarvittavia IAPWS:n suosittelemia yhtälöitä. Höyrystinputkessa kulloinkin vallitsevan virtausmuodon määrittämiseen käytetään sovelluskelpoisia virtausmuotojen välisiä rajoja kuvaavia yhtälöitä. Ohjelmassa käytetään painehäviön määritykseen kirjallisuudessa julkaistuja yhtälöitä, virtausmuodosta riippuen, alijäähtyneelle virtaukselle, kupla-, tulppa- ja rengasvirtaukselle sekä tulistetun höyryn virtaukselle. Ohjelman laskemia painehäviöarvioita verrattiin kirjallisuudesta valittuihin mittaustuloksiin. Laskettujen painehäviöiden virhe vaihteli välillä –19.5 ja +23.9 %. Virheiden itseisarvojen keskiarvo oli 12.8 %.

Mittausmenetelmien kehittaminen kuplakolonnille

Kuplakolonnireaktoreiden CFD-mallinnus on talla hetkella voimakkaasti kehittyva tutkimusalue. Kaksifaasivirtauksen luotettava simulointi ja mallintaminen on haastavaa kuplakolonnireaktorissa tapahtuvien ilmioiden monimutkaisuuden vuoksi. Reaktorin kayttaytymiseen vaikuttavat tekijat, kuten kolonnin hydrodynamiikka ja aineensiirto, tulee tuntea hyvin ennen mallien tekoa. Tassa tyossa on kokeellisesti tutkittu erilaisten mittausmenetelmien soveltuvuutta kuplakolonnin hydrodynamiikan tutkimiseen. Mittausmenetelmissa on keskitytty erityisesti CFD-mallien vaatimiin paikallisiin mittauksiin. Lisaksi tyossa on arvioitu mittausmenetelmien soveltuvuutta j a luotettavuutta CFD-mallien validointiin. Tyon kirjallisuusosassa on perehdytty kuplakolonnireaktorin hydrodynaamiseen kayttaytymiseen ja siihen vaikuttaviin tekijoihin. Naita ovat mm. reaktorityypit, kaasun dispergointi, virtaustyypit ja -alueet, kaasun tilavuusosuus, kaasukuplan koko ja kuplan nousunopeus. Mittauksia tehtiin kahdessa erikokoisessa kuplakolonnissa, joista pienemman halkaisija oli 0,078 m ja suuremman 0,182 m. Molempien kolonnien nestepinnan korkeus oli 4,62 m. Mittaukset tehtiin vesijohtovedella ja epaorgaanisella prosessiliuoksella. Hydrodynaamisista ominaisuuksista mitattiin kaasun tilavuusosuus, kaasukuplan koko seka kaasukuplan nousunopeus. Kaasun tilavuusosuusmittaukset tehtiin paaasiassa paine-eromittauksella ja joissakin tapauksissa pinnanmittausmenetelmalla. Kuplakoko- ja kuplan nousunopeusmittaukset tehtiin suumopeusvideokameralla ja laser Doppler-anemometrilla. Mittauksissa kaytettiin kahdeksaa erilaista kaasunjakolaitetta, joilla selvitettiin kaasunjakolaitteen ominaisuuksien vaikutusta kolonnin hydrodynamiikkaan. Tuloksista havaittiin, etta nestefaasin ominaisuuksilla oli suuri vaikutus kolonnin hydrodynaamiseen kayttaytymiseen. En kaasunjakolaitteilla vesijohtovedella mitatut hydrodynaamiset ominaisuudet eivat poikenneet paljoa toisistaan, kun taas prosessiliuoksella kaasunjakolaitteiden valille saatiin huomattavat erot. Mittausmenetelmista laser Doppler-anemometri ei kaytettavissa olleella optiikalla soveltunut kaasukuplien mittaamiseen. Kuplat olivat menetelmalle liian suuria. Suumopeusvideokamerallaja paine-eromittauksella paastiin hyviin tuloksiin.

Extração em fase sólida (SPE) e micro extração em fase sólida (SPME) de piretróides em água

The pyrethroids bifenthrin, permethrin, cypermethrin and deltamethrin were extracted by solid phase extraction (SPE) and solid phase microextraction (SPME). The analysis were performed on a gas chromatograph with electron capture detection (GC-ECD). Octadecil Silano-C18, Florisil and Silica stationary phases were studied for SPE. Better results were obtained for Florisil which gave recoveries from 80% to 108%. Pyrethroids extraction by SPME showed a linear response and a detection limit of 10 pg ml-1. Although the data showed that the two extraction methods were able to isolate the pesticide residues from water samples, the best results were obtained by using SPME which is more sensitive, faster, cheeper, being a more useful technique for the analysis of pyrethroids in drinking water.

Phase behavior and rheological analysis of reverse liquid crystals and W/I2, W/H2 gel emulsions using an amphiphilic block copolymer.

This article reports the phase behavior determi- nation of a system forming reverse liquid crystals and the formation of novel disperse systems in the two-phase region. The studied system is formed by water, cyclohexane, and Pluronic L-121, an amphiphilic block copolymer considered of special interest due to its aggregation and structural proper- ties. This system forms reverse cubic (I2) and reverse hexagonal (H2) phases at high polymer concentrations. These reverse phases are of particular interest since in the two-phase region, stable high internal phase reverse emulsions can be formed. The characterization of the I2 and H2 phases and of the derived gel emulsions was performed with small-angle X-ray scattering (SAXS) and rheometry, and the influence of temperature and water content was studied. TheH2 phase experimented a thermal transition to an I2 phase when temperature was increased, which presented an Fd3m structure. All samples showed a strong shear thinning behavior from low shear rates. The elasticmodulus (G0) in the I2 phase was around 1 order of magnitude higher than in theH2 phase. G0 was predominantly higher than the viscousmodulus (G00). In the gel emulsions,G0 was nearly frequency-independent, indicating their gel type nature. Contrarily to water-in-oil (W/O) normal emulsions, in W/I2 and W/H2 gel emulsions, G0, the complex viscosity (|η*|), and the yield stress (τ0) decreased with increasing water content, since the highly viscous microstructure of the con- tinuous phase was responsible for the high viscosity and elastic behavior of the emulsions, instead of the volumefraction of dispersed phase and droplet size. A rheological analysis, in which the cooperative flow theory, the soft glass rheology model, and the slip plane model were analyzed and compared, was performed to obtain one single model that could describe the non-Maxwellian behavior of both reverse phases and highly concentrated emulsions and to characterize their microstructure with the rheological properties.

Alternativas verdes para o preparo de amostra e determinação de poluentes fenólicos em água

The restricted availability of water sources suitable for consumption and high costs for obtaining potable water has caused an increase of the conscience concerning the use. Thus, there is a high demand for "environmentally safe methods" which are according to the principles of Green Chemistry. Moreover, these methods should be able to provide reliable results for the analysis of water quality for various pollutants, such as phenol. In this work, greener alternatives for sample preparation for phenol determination in aqueous matrices are presented, which include: liquid phase microextraction, solid phase microextraction, flow analysis, cloud point extraction and aqueous two-phase systems.

Computational studies for the design of process equipment with complex geometries

This study combines several projects related to the flows in vessels with complex shapes representing different chemical apparata. Three major cases were studied. The first one is a two-phase plate reactor with a complex structure of intersecting micro channels engraved on one plate which is covered by another plain plate. The second case is a tubular microreactor, consisting of two subcases. The first subcase is a multi-channel two-component commercial micromixer (slit interdigital) used to mix two liquid reagents before they enter the reactor. The second subcase is a micro-tube, where the distribution of the heat generated by the reaction was studied. The third case is a conventionally packed column. However, flow, reactions or mass transfer were not modeled. Instead, the research focused on how to describe mathematically the realistic geometry of the column packing, which is rather random and can not be created using conventional computeraided design or engineering (CAD/CAE) methods. Several modeling approaches were used to describe the performance of the processes in the considered vessels. Computational fluid dynamics (CFD) was used to describe the details of the flow in the plate microreactor and micromixer. A space-averaged mass transfer model based on Fick’s law was used to describe the exchange of the species through the gas-liquid interface in the microreactor. This model utilized data, namely the values of the interfacial area, obtained by the corresponding CFD model. A common heat transfer model was used to find the heat distribution in the micro-tube. To generate the column packing, an additional multibody dynamic model was implemented. Auxiliary simulation was carried out to determine the position and orientation of every packing element in the column. This data was then exported into a CAD system to generate desirable geometry, which could further be used for CFD simulations. The results demonstrated that the CFD model of the microreactor could predict the flow pattern well enough and agreed with experiments. The mass transfer model allowed to estimate the mass transfer coefficient. Modeling for the second case showed that the flow in the micromixer and the heat transfer in the tube could be excluded from the larger model which describes the chemical kinetics in the reactor. Results of the third case demonstrated that the auxiliary simulation could successfully generate complex random packing not only for the column but also for other similar cases.

Influence of multi-phase phenomena on semibatch crystallization processes of aqueous solutions

Crystal properties, product quality and particle size are determined by the operating conditions in the crystallization process. Thus, in order to obtain desired end-products, the crystallization process should be effectively controlled based on reliable kinetic information, which can be provided by powerful analytical tools such as Raman spectrometry and thermal analysis. The present research work studied various crystallization processes such as reactive crystallization, precipitation with anti-solvent and evaporation crystallization. The goal of the work was to understand more comprehensively the fundamentals, phenomena and utilizations of crystallization, and establish proper methods to control particle size distribution, especially for three phase gas-liquid-solid crystallization systems. As a part of the solid-liquid equilibrium studies in this work, prediction of KCl solubility in a MgCl2-KCl-H2O system was studied theoretically. Additionally, a solubility prediction model by Pitzer thermodynamic model was investigated based on solubility measurements of potassium dihydrogen phosphate with the presence of non-electronic organic substances in aqueous solutions. The prediction model helps to extend literature data and offers an easy and economical way to choose solvent for anti-solvent precipitation. Using experimental and modern analytical methods, precipitation kinetics and mass transfer in reactive crystallization of magnesium carbonate hydrates with magnesium hydroxide slurry and CO2 gas were systematically investigated. The obtained results gave deeper insight into gas-liquid-solid interactions and the mechanisms of this heterogeneous crystallization process. The research approach developed can provide theoretical guidance and act as a useful reference to promote development of gas-liquid reactive crystallization. Gas-liquid mass transfer of absorption in the presence of solid particles in a stirred tank was investigated in order to gain understanding of how different-sized particles interact with gas bubbles. Based on obtained volumetric mass transfer coefficient values, it was found that the influence of the presence of small particles on gas-liquid mass transfer cannot be ignored since there are interactions between bubbles and particles. Raman spectrometry was successfully applied for liquid and solids analysis in semi-batch anti-solvent precipitation and evaporation crystallization. Real-time information such as supersaturation, formation of precipitates and identification of crystal polymorphs could be obtained by Raman spectrometry. The solubility prediction models, monitoring methods for precipitation and empirical model for absorption developed in this study together with the methodologies used gives valuable information for aspects of industrial crystallization. Furthermore, Raman analysis was seen to be a potential controlling method for various crystallization processes.

Flow in porous media of oil-water systems

Fluid flow behaviour in porous media is a conundrum. Therefore, this research is focused on filtration-volumetric characterisation of fractured-carbonate sediments, coupled with their proper simulation. For this reason, at laboratory rock properties such as pore volume, permeability and porosity are measured, later phase permeabilities and oil recovery in function of flow rate are assessed. Furthermore, the rheological properties of three oils are measured and analysed. Finally based on rock and fluid properties, a model using COMSOL Multiphysics is built in order to compare the experimental and simulated results. The rock analyses show linear relation between flow rate and differential pressure, from which phase permeabilities and pressure gradient are determined, eventually the oil recovery under low and high flow rate is established. In addition, the oils reveal thixotropic properties as well as non-Newtonian behaviour described by Bingham model, consequently Carreau viscosity model for the used oil is given. Given these points, the model for oil and water is built in COMSOL Multiphysics, whereupon successfully the reciprocity between experimental and simulated results is analysed and compared. Finally, a two-phase displacement model is elaborated.

Wormlike micelle formation and flow alignment of a pluronic block copolymer in aqueous solution

The self-assembly into wormlike micelles of a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymer Pluronic P84 in aqueous salt solution (2 M NaCl) has been studied by rheology, small-angle X-ray and neutron scattering (SAXS/SANS), and light scattering. Measurements of the flow curves by controlled stress rheometry indicated phase separation under flow. SAXS on solutions subjected to capillary flow showed alignment of micelles at intermediate shear rates, although loss of alignment was observed for high shear rates. For dilute solutions, SAXS and static light scattering data on unaligned samples could be superposed over three decades in scattering vector, providing unique information on the wormlike micelle structure over several length scales. SANS data provided information on even shorter length scales, in particular, concerning "blob" scattering from the micelle corona. The data could be modeled based on a system of semiflexible self-avoiding cylinders with a circular cross-section, as described by the wormlike chain model with excluded volume interactions. The micelle structure was compared at two temperatures close to the cloud point (47 degrees C). The micellar radius was found not to vary with temperature in this region, although the contour length increased with increasing temperature, whereas the Kuhn length decreased. These variations result in an increase of the low-concentration radius of gyration with increasing temperature. This was consistent with dynamic light scattering results, and, applying theoretical results from the literature, this is in agreement with an increase in endcap energy due to changes in hydration of the poly(ethylene oxide) blocks as the temperature is increased.

Non-invasive strategy in assessing asthma through biofluids metabolomics exploration: exhaled breath and urine potentialities

Asthma is a significant health issue in the pediatric population with a noteworthy growth over the years. The proposed challenge for this PhD thesis was the development of advanced methodologies to establish metabolomic patterns in urine and exhaled breath associated with asthma whose applicability was subsequently exploited to evaluate the disease state, the therapy adhesion and effect and for diagnostic purposes. The volatile composition of exhaled breath was studied combining headspace solid phase microextraction (HS-SPME) with gas chromatography coupled to mass spectrometry or with comprehensive two-dimensional gas chromatography coupled to mass spectrometry with a high resolution time of flight analyzer (GC×GC–ToFMS). These methodologies allowed the identification of several hundred compounds from different chemical families. Multivariate analysis (MVA) led to the conclusion that the metabolomic profile of asthma individuals is characterized by higher levels of compounds associated with lipid peroxidation, possibly linked to oxidative stress and inflammation (alkanes and aldehydes) known to play an important role in asthma. For future applications in clinical settings a set of nine compounds was defined and the clinical applicability was proven in monitoring the disease status and in the evaluation of the effect and / or adherence to therapy. The global volatile metabolome of urine was also explored using an HSSPME/GC×GC–ToFMS method and c.a. 200 compounds were identified. A targeted analysis was performed, with 78 compounds related with lipid peroxidation and consequently to oxidative stress levels and inflammation. The urinary non-volatile metabolomic pattern of asthma was established using proton nuclear magnetic resonance (1H NMR). This analysis allowed identifying central metabolic pathways such as oxidative stress, amino acid and lipid metabolism, gut microflora alterations, alterations in the tricarboxylic acid (TCA) cycle, histidine metabolism, lactic acidosis, and modification of free tyrosine residues after eosinophil stimulation. The obtained results allowed exploring and demonstrating the potential of analyzing the metabolomic profile of exhaled air and urine in asthma. Besides the successful development of analysis methodologies, it was possible to explore through exhaled air and urine biochemical pathways affected by asthma, observing complementarity between matrices, as well as, verify the clinical applicability.

Desenvolvimento de uma unidade pirolítica com reator de cilindro rotativo: obtenção de bio-óleo

The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil.

Um sistema para estimação da vazão de gás de poços produzindo por Plunger Lift para vaso separador de teste em plataformas de petróleo

This work intends to analyze the behavior of the gas flow of plunger lift wells producing to well testing separators in offshore production platforms to aim a technical procedure to estimate the gas flow during the slug production period. The motivation for this work appeared from the expectation of some wells equipped with plunger lift method by PETROBRAS in Ubarana sea field located at Rio Grande do Norte State coast where the produced fluids measurement is made in well testing separators at the platform. The oil artificial lift method called plunger lift is used when the available energy of the reservoir is not high enough to overcome all the necessary load losses to lift the oil from the bottom of the well to the surface continuously. This method consists, basically, in one free piston acting as a mechanical interface between the formation gas and the produced liquids, greatly increasing the well s lifting efficiency. A pneumatic control valve is mounted at the flow line to control the cycles. When this valve opens, the plunger starts to move from the bottom to the surface of the well lifting all the oil and gas that are above it until to reach the well test separator where the fluids are measured. The well test separator is used to measure all the volumes produced by the well during a certain period of time called production test. In most cases, the separators are designed to measure stabilized flow, in other words, reasonably constant flow by the use of level and pressure electronic controllers (PLC) and by assumption of a steady pressure inside the separator. With plunger lift wells the liquid and gas flow at the surface are cyclical and unstable what causes the appearance of slugs inside the separator, mainly in the gas phase, because introduce significant errors in the measurement system (e.g.: overrange error). The flow gas analysis proposed in this work is based on two mathematical models used together: i) a plunger lift well model proposed by Baruzzi [1] with later modifications made by Bolonhini [2] to built a plunger lift simulator; ii) a two-phase separator model (gas + liquid) based from a three-phase separator model (gas + oil + water) proposed by Nunes [3]. Based on the models above and with field data collected from the well test separator of PUB-02 platform (Ubarana sea field) it was possible to demonstrate that the output gas flow of the separator can be estimate, with a reasonable precision, from the control signal of the Pressure Control Valve (PCV). Several models of the System Identification Toolbox from MATLAB® were analyzed to evaluate which one better fit to the data collected from the field. For validation of the models, it was used the AIC criterion, as well as a variant of the cross validation criterion. The ARX model performance was the best one to fit to the data and, this way, we decided to evaluate a recursive algorithm (RARX) also with real time data. The results were quite promising that indicating the viability to estimate the output gas flow rate from a plunger lift well producing to a well test separator, with the built-in information of the control signal to the PCV

Modal representation of three-phase lines applying two transformation matrices: Evaluation of its eigenvectors

The objective of this paper is to show an alternative representation in time domain of a non-transposed three-phase transmission line decomposed in its exact modes by using two transformation matrices. The first matrix is Clarke's matrix that is real, frequency independent, easily represented in computational transient programs (EMTP) and separates the line into Quasi-modes alpha, beta and zero. After that, Quasi-modes a and zero are decomposed into their exact modes by using a modal transformation matrix whose elements can be synthesized in time domain through standard curve-fitting techniques. The main advantage of this alternative representation is to reduce the processing time because a frequency dependent modal transformation matrix of a three-phase line has nine elements to be represented in time domain while a modal transformation matrix of a two-phase line has only four elements. This paper shows modal decomposition process and eigenvectors of a nontransposed three-phase line with a vertical symmetry plane whose nominal voltage is 440 kV and line length is 500 km.