The overall aim of this project was to study 'functionalised' calcium carbonates (FCCs) for use as a carrier for the controlled release of 'actives,' by permeation and diffusion, and is being proposed as an environmentally friendly and non-toxic pharmaceutical excipient, nutraceutical, and flavour carrier. The delivery of a drug to its target site in the appropriate amount and time-frame in order for it to have a controlled release effect whilst achieving the maximum therapeutic effect remains a topic of design and development for novel drug delivery systems. FCCs encompass a family of new pharmaceutical excipients in which the conditions of manufacture follow strict process regulations with respect to the grade of reagents that are employed and the microbiological environment under which they are produced, and include freedom from organic polymers. Adjustments to the FCC production process can be used to produce a wide range of different morphologies, and raise the possibility of tailoring the void structures of the particles to provide controlled release delivery vehicles for actives across many fields, including drugs and flavours. However, such tailoring can only be fully optimised by a fundamental characterisation of the way in which a drug, loaded into an FCC, then flows and diffuses out over a period of time to provide the delayed release. It was found that adsorption on the FCC surface is selective, for example, saccharin does not become adsorbed from 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES) buffer solution, and neither does anethole from ethanol. FCC also does not adsorb the cationic probe benzyltrimethylammonium bromide (BTMAB) or the anionic probe sodium 2-naphthalenesulphonate (Na2NS). However, it was found that vanillin adsorbs onto the FCC in an amount of 2.00 ± 0.59 mg g^-1. Aspirin and vanillin adsorption from ethanolic solutions with various additions of water onto FCC TP was investigated and fitted with the Tóth isotherm. It was estimated that vanillin adsorbed onto around 17 %, and aspirin onto around 39 %, of the overall FCC TP surface area without the addition of any water. An equation was formulated in order to approximate the adsorption as a function of the FCC's surface coverage by the water. This is discussed in Chapter 4 and has also been published in a peer-reviewed academic journal (Levy et al., 2017). Chapter 5 discusses the preliminary steps of the loading of vanillin and saccharin into FCC, and the results were inconclusive for a majority of samples, concluding that the loading and analysis methods need refining. The modelling of the diffusion profiles of vanillin loaded FCC S07 and S10 was successful, and resulted in diffusion coefficients of 231.9 x 10^-16 m^2 s^-1 and 248.44 x 10^-16 m^ s^-1, respectively. This is outlined in Chapter 6. Chapter 7 describes the 'zero length column' (ZLC) technique, which was used as a way to characterise the diffusivity of the intraparticle pores of each FCC grade. However, it was established that there are many experimental artefacts present with such a method. This work outlines the development of the novel 'finite length column' (FLC), which was developed as a means to overcome the limitations of the ZLC (Levy et al., 2015). Effective diffusivity coefficients in the long-term region of the diffusion curves of the FCC samples range from 1.06-106 x 10 ^-16 m ^2 s^-1. The FLC was then used in preliminary trials to dilute FCC with an inert solid in order to further refine the ZLC technique, and is discussed in Chapter 8. Two mathematical methods were also developed to aid in the refinement. The reported effective diffusivity coefficient for FCC 03 in the long-term region of the diffusion curve is 49.5 x 10^-16 m^2 s^-1. In conclusion, this work confirms that FCC has potential for use as a carrier for the controlled release of 'actives' by diffusion. The utilisation of mathematical modelling in conjunction with experimental methods in the study of drug release and delivery is steadily increasing due to its enormous future potential; it will enable the optimisation of novel dosage forms and the elucidation of release mechanisms at a major reduction in cost and time compared with the number of experimental studies required to do so.

My diploma theisis is focused on design and assessment of structural systém of industrial building in tended for livestock farming. The design is processed in two options. Both oft hem has the same dimensions but cross sections of the supporting elements are changed. Floor plan of the first part is a rectangular shape, dimension is 29,28 m x 24,8 m. Floor plan of the second part is a rectangular shape, dimension is 161,18 m x 46,8 m. Slope of saddle roof is 18°.

The target of diploma thesis was to improve author’s theoretical and practical design knowledge of process engineering. In the diploma thesis a Simplified Basic Engineering Project of distillation unit has been developed. It was necessary to become familiar with the process technology and formal requirements of Basic Engineering Project. The most important parts of Basic Engineering Project are material and heat balances. Material and heat balances are the corner stones of distillation unit equipment design. Parameters of process equipment are presented in the form of equipment datasheets. The specification of pipelines is based on material and heat balances too. Inevitable part of Basic Engineering are Process Flow Diagram and Piping and Instrumentation Diagram (PFD & PID). Process Flow Diagram and Piping and Instrumentation Diagram include all equipment, piping and basic control loops.

No description available.

Die Verfügbarkeit neuer Technologien wie Multi-Core, SSD oder große Hauptspeicherkapazitäten bieten eine Gelegenheit, die klassischen Architekturansätze von Datenbanksystemen zu überdenken und an bestimmten Stellen zu korrigieren. In diesem Beitrag stellen wir die Grobstruktur der neuen hauptspeicherzentrierten SAP Technologie als einen Ansatz einer kommerziellen Umsetzung moderner Architekturkonzepte vor. Zentrales Design-Kriterium ist dabei ein hybrider Ansatz, um eine möglichst hohe Anzahl von Anforderungsvarianten optimal zu unterstützen. Nach einer Einleitung führt der Artikel durch die wichtigsten Architekturkomponenten und illustriert den grundsätzlichen Aufbau des Systems. Für einen „deep dive“ werden zwei Bereiche in Teil 3 und 4 des Artikels im Detail diskutiert. Dabei greift der Artikel zum einen den Aspekt der physischen Optimierung im Kontext eines hauptspeicherzentrierten Systems auf und diskutiert unterschiedliche Komprimierungs- und Sortierungskriterien, wie sie im klassischen disk-zentrierten Ansatz nicht zu finden sind. Zum anderen wird die Unterstützung von Planungsanwendungen skizziert, wodurch ein Einblick in die spezifische Unterstützung einer Anwendungsdomäne („business planning“) und die prinzipiellen Erweiterungen für komplexe Operationen zur direkten Unterstützung von darauf aufbauender Planungsfunktionalität gezeigt werden.

Ce travail contribue aux efforts de l'Union Européenne pour réduire les émissions de CO2. Son objectif est d'aider les industries produisant de la chaleur fatale à récupérer cette énergie perdue, d'augmenter sa température et de la réutiliser in situ. Les transformateurs de chaleur (Absorption Heat Transformers ou AHT), machines à absorption consommant très peu d'électricité, sont alors ici étudiés. Les AHTs existants rencontrent des problèmes comme la corrosion, la cristallisation, la toxicité et les niveaux de pression éloignés de la pression atmosphérique. Ceux-ci sont causés par les fluides conventionnels (Eau/LiBr et Ammoniaque/Eau) et s'aggravent à des températures supérieures à 120°C. Des modèles de conception ainsi que des solutions techniques, applicables avec tous mélanges de fluides organiques, sont alors proposés dans cette thèse. Ces modèles sont validés avec des données de la littérature et implémentés dans des outils d'aide à la décision.Tout d'abord, un modèle de sélection de paires de fluides organiques (parmi une liste de fluides) est développé. Les contraintes prises en compte sont, entre autres, les types et les profils de températures des sources et puits de chaleur, et les propriétés du fluide. Pour chaque type de fluide, la méthode la plus adaptée au calcul des propriétés physiques des fluides est choisie.En second lieu, pour effectuer la séparation des 2 constituants du mélange de fluides organiques, le générateur (composant recevant la chaleur fatale) et le condenseur de l'AHT sont fusionnés pour former une colonne de distillation. Un modèle d'une colonne de distillation nommée « hybride » est alors développé en adaptant la méthode de Ponchon-Savarit et en la combinant avec la méthode ETD (Equal Thermodynamic Distance). Cette colonne associe les avantages des 2 types de colonnes adiabatiques et diabatiques. Elle allie réduction de production d'entropie et meilleure exploitation des sources de chaleur à températures glissantes. La conception mécanique de la colonne hybride est aussi incluse.Troisièmement, pour atteindre la température théorique maximale du mélange de fluide déjà choisi, l'absorbeur de l'AHT (où la chaleur à haute température est libérée) est divisé en sections adiabatiques suivies par des sections diabatiques. De plus, les modèles détaillés des colonnes à bulles (fonctionnant en co-courant ou en contre-courant) ainsi que de la colonne à garnissage sont présentés et comparés entre eux.Les principaux résultats de ces travaux consistent en une nouvelle méthodologie de choix de fluides organiques pouvant remplacer les mélanges classiques surtout à températures élevées (supérieures à 130 °C). En ce qui concerne la colonne de distillation, il est montré que la colonne adiabatique constitue un meilleur choix lorsqu'une source de chaleur latente est disponible tandis qu'avec une source de chaleur sensible, la colonne hybride engendre moins de pertes exergétiques. En passant à l'absorbeur, le nouveau mode d'opération de celui-ci permet à l'utilisateur d'atteindre des températures plus élevées que celles réalisées avec les technologies actuellement disponibles. Enfin, les modèles développés permettent de choisir les technologies de distillation (adiabatique, diabatique ou hybride) et d'absorption (colonne à bulles ou à garnissage) les plus appropriées en s'adaptant à différentes problématiques industrielles. / This work is part of the European union efforts to reduce its CO2 emissions. It aims to assist any waste heat producing industry in recuperating this lost thermal energy, pumping it to higher temperature levels and reusing it on site. Absorption Heat Transformers (AHT), that consume little electricity, are used for this task. Current AHT problems such as corrosion, crystallization, toxicity and inconvenient pressure levels are caused by conventionally used H2O/LiBr and NH3/ H2O working fluids and get worse at temperatures exceeding 120°C. Potential solutions are thus suggested. According to them, models are developed; they are all able to operate with any organic mixture and are customized to accompany the industrialist from start to finish. These solutions were validated by comparing them with literature data and are implemented into several tools.Firstly, a model selects the optimal organic binary mixture -among a list of fluids- in terms of the real case application's constraints: Heat transfer fluids used, Heat source's and heat sink's types and temperature profiles, mixtures transport properties among other parameters. Suitable thermodynamic model is selected for different fluid group types.Secondly, in order to separate the 2 components of the chosen mixture of organic compounds, the AHT generator (component which receives waste heat) is merged with the AHT condenser thus forming a distillation column. A “hybrid column” is designed by modifying the Ponchon-Savarit method and combining it with the Equal Thermodynamic Distance (ETD) method. This new column associates the best features of the two columns. It reduces entropy production rates and best exploits temperature gliding heat sources. Mechanical design for the hybrid column is also included.Thirdly, to ensure that the maximum theoretical temperature of the working fluid is reached, the AHT absorber (where high temperature heat is released) is divided into consecutive adiabatic parts followed by diabatic ones. Detailed Models for co-current and counter-current bubble columns as well as packing columns are presented and compared.Main results consist in a selection methodology of organic compounds mixtures, capable of replacing conventional ones specially at temperatures higher than 130 °C. It's also shown that adiabatic columns are better options when latent type heat sources are available while hybrid columns lose less exergy when used with sensible heat sources. As for the absorber, the new operating mode provides the user with higher temperatures than currently reached by available technologies. Finally, using the developed models, tailored and most suitable distillation (adiabatic, diabatic or hybrid columns) and absorber (bubble or packing columns) technologies can be proposed depending on the industrial specific cases and requirements.

[pt] Esta dissertação estuda formulações, algoritmos e métodos exatos para resolver instâncias do Problema de Alocação Generalizada (PAG) com uma separação de desigualdades (3, 0.5)-SRC que viabilize a enumeração de colunas. Este trabalho é motivado pela perspectiva de alcançar o estado-da-arte com resultados competitivos comparáveis às melhores soluções encontradas na literatura por Avella (2010) e Michelon (2012). A pesquisa abrange métodos exatos e heurísticas, com ênfase no estudo que aborda a decomposição de Dantzig-Wolfe, o algoritmo de geração de colunas, a estabilização de colunas por meio da ponderação de duais proposto por Wentges (1997) e a enumeração de colunas habilitada pela minimização do gap decorrente do algoritmo de price-and-cut. O algoritmo de price-and-cut desenvolvido recorre à geração de colunas (pricing) aliada à separação de (3, 0.5)-SRCs para aumentar o lower bound gerado, assim minimizando o gap. A geração de colunas implementada é inspirada no algoritmo de Savelsbergh (1997); e a separação de (3, 0.5)-SRCs é motivada pelo trabalho de Jepsen (2008) e pelo algoritmo branch-cut-andprice proposto por Poggi e Uchoa (2016) para o CVRP. De acordo com os experimentos computacionais, as desigualdades adotadas são capazes de reduzir o gap suficientemente para viabilizar a enumeração de colunas em diversas instâncias do PAG com até 200 tarefas e 20 máquinas. O método utilizado obteve resultados compatíveis às melhores soluções conhecidas, enumerando todas as colunas necessárias para cobrir o gap determinado pelo price-and-cut. Esse resultado incentiva futuras pesquisas para estender a aplicação do algoritmo a instâncias maiores e mais difíceis. / [en] This dissertation deals with formulations, algorithms and exact methods for solving the well-known Generalized Assignment Problem (GAP) through a price-and-cut approach with the separation of (3, 0.5)-SRC inequalities in order to improve column enumeration feasibility and efficiency. This work is motivated by the perspective of reaching state-of-the-art performance, attaining competitive results which are comparable with the best known solutions found in the literature by Avella (2010) and Michelon (2012). This research was build on exact methods and some heuristics with emphasis on the Dantzig- Wolfe decomposition, the column generation algorithm, the stabilization through weighted Dantzig-Wolfe decomposition proposed byWentges (1997) and finally the column enumeration motivated by the gap minimization reached through the price-and-cut algorithm. The price-and-cut algorithm proposed here resort to column generation (pricing) combined with the separation of (3, 0.5)-SRC cuts in order to increase the generated lower bound, thus minimizing the attained gap. This column generation algorithm follows the work of Savelsbergh (1997); and the separation of (3, 0.5)-SRCs is formulated by Jepsen (2008) and motivated by the branch-cut-and-price algorithm proposed by Poggi and Uchoa (2016) for the CVRP. According to computational experiments, the adopted inequalities are capable of sufficiently reducing the gap, assuring the feasibility of column enumeration for several GAP instances with up to 200 tasks and 20 machines. This method achieved expressive results, compatible with the best known solutions, enumerating all the necessary columns to cover the gap found by the price-and-cut. Therefore, these results motivate future research towards the extension of the method s applicability to larger and more complex instances.

No description available.

O interesse por técnicas analíticas que ofereçam a sensibilidade adequada, que sejam econômicas, ambientalmente corretas e capazes de processar rapidamente um grande número de amostras de diferentes complexidades é cada vez maior. Nesse aspecto, a utilização da LC no modo multidimensional é alternativa promissora, especialmente quando estratégias de extração e pré-concentração em fase sólida acopladas de forma on-line com a separação são exploradas, tanto em escala convencional quanto em escala miniaturizada. A ocorrência ambiental de contaminantes emergentes (EDCs) e seus impactos nas formas de vida aquática e terrestre têm sido motivo de preocupação. A quantificação desses analitos no ambiente exige métodos com limites de detecção (LDs) muito baixos, fazendo das estratégias column switching, com a inerente pré-concentração on-line, pertinentes para satisfazer as exigências na determinação desses compostos. Nesse cenário, o desenvolvimento e avaliação de estratégias column switching para determinação de contaminantes emergentes em amostras de interesse ambiental como aplicação modelo no estudo comparativo entre as escalas convencional e miniaturizada se faz impactante. Várias estratégias abrangendo column switching capilar e convencional foram investigadas. Colunas extratoras preenchidas com fases comerciais foram avaliadas, e tiveram seu desempenho testado no acoplamento com diversas colunas analíticas. Métodos em column switching capilar e convencional foram desenvolvidos e validados, tendo sido avaliadas as principais figuras de mérito. Os LQs atingidos em CS-UHPLC-ESI-MS/MS variaram de 0,001 ng mL-1 (BP e BzP) a 0,1 ng mL-1 (E3, E2 e EE2); para o método CS-cLC-ESI-MS/MS, os LQs foram maiores, variando entre 0,008 ng mL-1 (BP e BzP) a 0,8 ng mL-1 (E3, E2 e EE2). A linearidade dos métodos foi atestada avaliando-se os gráficos de resíduos, coeficiente de determinação e aplicando-se ponderações quando pertinente. A exatidão e a precisão foram investigadas, apresentando valores dentro dos critérios de aceitação. Por fim, os métodos foram aplicados em amostras ambientais aquosas coletadas em São Carlos - SP, mostrando que os métodos são adequados ao fim a que se destinam. / The interest in analytical techniques that offer adequate sensitivity, that are economical, environmentally friendly and capable of rapidly processing many samples of different complexities is increasing. In this regard, the use of LC in the multidimensional mode is a promising alternative, especially when solid phase extraction and preconcentration strategies coupled online with the separation are explored, both on a conventional scale and on a miniaturized scale. The environmental occurrence of emerging pollutants (EDCs) and their impacts on aquatic and terrestrial life forms have been of concern. Quantification of these analytes in the environment requires methods with very low detection limits (LDs), making column switching strategies with the inherent preconcentration online relevant to satisfy the requirements in determining these compounds. In this scenario, the development and evaluation of column switching strategies for the determination of emerging contaminants in samples of environmental interest as an application model in the comparative study between conventional and miniaturized scales is striking. Several strategies covering capillary and conventional column switching were investigated. Extraction columns filled with commercial phases were evaluated, and their performance was tested in the coupling with several analytical columns. Methods in capillary and conventional column switching modes were developed and validated, and the main figures of merit were evaluated. The LQs reached in CS-UHPLC-ESI-MS / MS ranged from 0.001 ng mL-1 (BP and BzP) to 0.1 ng mL-1 (E3, E2 and EE2); for the CS-cLC-ESI-MS / MS method, the LQs were higher, ranging from 0.008 ng mL-1 (BP and BzP) to 0.8 ng mL-1 (E3, E2 and EE2). The linearity of the methods was attested by evaluating the residual plots, coefficient of determination and applying weighted calibration when needed. Accuracy and precision were investigated, presenting values within the acceptance criteria. Finally, the methods were applied in samples collected in São Carlos - SP, showing that the methods are suitable for the purpose.

Cette thèse projetait d’étudier à la fois l’hydrodynamique et le transfert de masse dans les colonnes de pulvérisation et les colonnes à bulles, et de comparer leurs consommations de puissance spécifiques afin d’élaborer la directive de sélection pour les utilisations industrielles. Les résultats ont indiqué que la colonne à bulles avait une surface interfaciale spécifique plus grande que la colonne de pulvérisation lorsqu’on utilise un faible taux de charge de gaz. Dans cette plage de fonctionnement, la colonne à bulles produisait un coefficient de transfert de masse global plus élevé avec la même consommation d'énergie spécifique. Cependant, lorsqu’elle fonctionnait à un taux de charge de gaz élevé, la colonne de pulvérisation était meilleure que la colonne à bulles, car celle-ci consommait une plus grande consommation d’énergie, la chute de pression de la colonne à bulles étant principalement due au débit de gaz. En outre, cette recherche a également étudié l'effet de la phase solide sur l'hydrodynamique et le transfert de masse dans la colonne à bulles et la colonne de pulvérisation. En utilisant la méthode colorimétrique de l'expérience «bouteille rouge», il a été constaté que la collision bulle-particules diminuait le transfert de masse des bulles car la collision ralentissait les bulles, en particulier pour les petites bulles, du fait que la petite bulle perdait simplement leur vitesses de la collision. Cependant, l’introduction des particules présentait un avantage, car les particules solides pouvaient obstruer la bulle en hausse et réduire sa vitesse de montée. En conséquence, le temps de contact entre le gaz et le liquide est augmenté et conduit à une plus grande rétention de gaz, une zone interfaciale spécifique et donc un transfert de masse. / This thesis projected to investigate both hydrodynamics and mass transfer in both spray and bubble columns and comparing their specific power consumptions in order to develop the selection guideline for industrial usages. The results indicated that the bubble column had larger specific interfacial area than the spray column when using a small gas loading rate. At this range of operation, the bubble column yielded a higher overall mass transfer coefficient with the same specific power consumption. However, when operating at high gas loading rate, the spray column was the one better than the bubble column since the bubble column consumed larger power consumption as the pressure drop of the bubble column was mostly due to the gas flow. In addition, this research also studied the effect of the solid phase on the hydrodynamics and mass transfer in the bubble column and spray column. By using the colorimetric method of “red bottle” experiment, it was found that the bubble-particles collision diminished the mass transfer of bubbles because the collision slowed down the bubbles especially for the small bubbles due to the fact that the small bubble simply lost their velocities from the collision. However, there was an advantage of introducing the particles since solid particles could obstruct the rising bubble and reduced its rising velocity. Consequently, the contact time between gas and liquid is increased and resulted in a higher gas hold up, specific interfacial area and thus mass transfer.