Dissertations / Theses on the topic 'Valorization process'

La production de l'hydrogène à partir de biomasse est actuellement à l'étude mais la méthode de valorisation du biogaz (mélange H2/CO2) par réactions catalytiques, autres que la simple combustion, n'a pas encore été retenue. Par conséquent, le principal objectif de ce travail est d'explorer les autres voies. L'effet du CO2 sur le système catalytique est mal connu et seulement un effet négatif sur la dissociation de l'hydrogène a été mentionné. L'hydrogénation du toluène sur un catalyseur Pt a d'abord été étudiée sans CO2 pour suivre son comportement et éventuellement sa perte d'activité. En présence de CO2, l'inactivité complète du catalyseur pour l'hydrogénation du toluène a été mis en évidence. La modification de la surface du catalyseur par le CO2 est quantifiée par DRIFT et un mécanisme à deux sites a été montré. La réaction de Reverse Water Gas Shift produisant du CO se trouve être la principale cause de la désactivation de la surface de catalyseur avec le CO2. Donc la compétition d'adsorption entre le CO et des acides carboxyliques a été mise à profit pour favoriser sélectivement la conversion des acides. Pour l'alumine, elle est polluée par des carbonates complexes venant du CO2. La silice étant aussi connue pour promouvoir la décomposition, ces supports ont été rejetés. L'oxyde de titane a été utilisé pour catalyser une autre gamme de produits. Sur ce catalyseur, le changement de sélectivité entre le RWGS et la conversion de l'acide a été observé. Quant à l'oxyde de fer (catalyseur moins actif), il n’est pas capable de produire du CO à partir du CO2. La chimie de surface de l'oxyde de fer joue un rôle important sur la sélectivité du produit parmi les cétones et les aldéhydes. Un mécanisme à deux sites peut réutiliser pour l'oxyde de fer, montrant qu'un fonctionnement stable peut être trouvé si la réduction par l'hydrogène est continue. Si l'oxyde de fer est totalement oxydé par le CO2, produit de réaction, la production des cétones cesse. Énergiquement, le procédé de production d'acétone peut être autosuffisant et l'acétone peut être utilisée comme une molécule de stockage d'énergie. Le procédé va aussi compenser le nouveau procédé de production de phénol qui ne produit pas l'acétone
Hydrogen potential from biomass is currently being studied but ways of valorization of such biogas (H2/CO2 mix) via catalytic reaction, other than simply burning has not yet been considered. Thus the main objective of this work is the exploration of such methods. Effect of CO2 over catalytic system was not well known and only hydrogen dissociation inhibition is reported. Toluene hydrogenation over Pt catalyst is studied and activity loss transition behavior is observed with no CO2 where as complete catalyst inactivity for toluene hydrogenation is found in presence of CO2. Catalyst surface change by CO2 is quantified by DRIFT analysis and two-site mechanism is found to prevail. Reverse water gas shift reaction producing CO is found to be the main cause behind such catalyst surface response to CO2. Adsorption competition between CO and carboxylic acids is exploited for selectivity shift in favor of acids conversion. Alumina support is fouled by carbonates complexes with CO2 while silica is reported to promote decomposition, thus both were rejected and titanium oxide is used instead with a range of products produced. The required selectivity shift between reverse water gas shift and acid conversion is thus observed. Less active iron oxide catalyst further suppresses CO2 conversion. Iron oxide surface chemistry plays an important role over product selectivity among ketones and aldehydes. Two sites mechanism still prevails over iron and stable continuous operation requires simultaneous iron reduction via hydrogen, if totally oxidized by CO2–a reaction product, will cease to produce ketones. Energetically the process devised for acetone production is self sufficient and acetone not only act as an energy storage molecule but can also compensate new phenol production process producing no acetone

Les nanoémulsions sont des formulations intéressantes pour des applications telles que les cosmétiques, les produits pharmaceutiques et les produits alimentaires. Elles peuvent être produites par des techniques à basse ou haute énergie. Dans ce travail, un procédé impliquant une pression modérée, l'émulsification membranaire par prémix a été proposé comme alternative. Des nanoémulsions huile-dans-eau (H/E) et eau-dans-huile (E/H) ont été produites avec une installation à l'échelle pilote composée d'un pousse-seringue à haute pression et d'une membrane Shirasu Porous Glass (SPG). Tout d'abord, l'influence des nombreux paramètres de procédé et de composition sur la taille des gouttelettes et la pression résultante a été étudiée avec des compositions modèles afin d'optimiser la production. Ainsi, des nanoémulsions H/E d'environ 260 nm et E/H d'environ 600 nm ont été produites avec succès. Puis, le montage a été utilisé pour produire des nanoémulsions de compositions spécifiques, des nanoémulsions H/E et E/H stabilisées avec des tensioactifs polypeptidiques et une nanoémulsion H/E adaptée à l'injection. Enfin, le procédé développé a été comparé à deux procédés à haute énergie traditionnels, le microfludiseur et les ultrasons en termes de taille des gouttelettes et de conservation d'actifs. Aucune différence entre les procédés n'a été observée en ce qui concerne la préservation de l'acif choisi. Cependant, en ce qui concerne la taille, les nanoémulsions produites par les membranes ont présenté des gouttelettes monodisperses de 335 nm par rapport aux autres procédés qui ont produit des nanoémulsions d'environ 150 nm de taille moyenne mais contenant aussi des gouttelettes de taille micrométrique détectées par diffraction laser et microscopie optique. Pour cette raison, les nanoémulsions produites par procédé membranaire conviennent également pour des applications parentérales sans étape de filtration supplémentaire
Nanoemulsions are interesting carriers for applications such as cosmetics, pharmaceutical and food. They are produced usually by low or high energy techniques. In this work, a process involving moderate pressure, premix membrane emulsification (PME) was proposed as an alternative. Oil-in-water (O/W) and water-in-oil (W/O) nanoemulsions were produced with a pilot scale set-up composed of a controlled high pressure syringe pump and Shirasu Porous Glass (SPG) membrane. First, the influence of process and composition parameters on droplet sizes and pressures was extensively studied with model compositions to optimize the production. Thus, nanoemulsions down to 260 nm for O/W and around 600 nm for W/O were successfully produced. Then, the set-up was used to produce nanoemulsions of specific compositions: O/W and W/O nanoemulsions stabilized with polypeptidic surfactants and O/W nanoemulsions suitable for injection. Finally, the set-up developed was compared to two traditional high energy processes, microfludizer and ultrasound in terms of droplet size and active preservation. No real difference between the three processes was seen on active preservation with the model active chosen. However, regarding droplet size, PME produced monodispersed droplets of 335 nm compared to the other processes which produced nanoemulsions of around 150 nm but with the presence of micron size droplets detected by laser diffraction and optical microscopy. Therefore, PME nanoemulsions are also suitable for parenterals applications with no additional filtration step required

The valorization of agro-industrial wastes represents a huge advantage for the transformation industry and the environment. Particularly, biomasses like spent coffee grounds are largely produced worldwide by coffee-based industries and do not require any pre-treatment for their use as raw material for extraction processes. Indeed, exhaust coffee grounds are usually collected in separated containers, either in coffee shops either in vending machines and are already in powder form. Several authors, analyzing chemical composition of spent coffee grounds, demonstrated their potential use as natural source of antioxidants, which are molecules that can find several applications in food, pharmaceutical and cosmetic industries. In the first chapter of this work, a brief introduction on the biorefinery concept and proposed reuses of spent coffee grounds, based on literature data, were exposed, focusing the attention on the main valuable step of a potential biorefinery based on coffee: the recovery of high added-value compounds from exhaust coffee by green and innovative techniques and methods finalized to preserve their bioactivity. The antioxidant activity of spent coffee grounds can be traced back to polyphenols, like chlorogenic acid and its isomers, its derivatives, and melanoidins. The antioxidant activity and type of antioxidants that are recoverable from exhaust coffee powder, as well as its chemical composition, are functions of the type of raw material (e.g. Coffea arabica, Coffea canephora), but also the brewing process used for beverage preparation. In this thesis, spent coffee grounds collected by common vending machines, were subjected to a preliminary characterization, whose results were reported in chapter 2, and to a study on different extraction techniques (solid-liquid extraction, high- pressure and temperature-assisted extraction, microwave-assisted extraction and continuous pressurized ultrasound-assisted extraction), solvents, and operating conditions. Indeed, one of the main aims of this research project was to perform the antioxidant recovery from SCG by using green solvents as water-ethanol solutions and to improve the extraction yields by working on the other process variables. A study on the recovery of antioxidants by microwave-assisted extraction was carried out in chapter 3, evaluating process optimization, extraction kinetics and the potential use of the extract for cosmetic purposes. For the study, both response surface modeling and kinetic studies were employed as tools for process optimization and the extracts were evaluated in terms of total polyphenol yield, total flavonoid yield and antiradical power. Chapter 5 deals with the utilization of high pressure and temperature-assisted extraction for antioxidant recovery from spent coffee grounds, while continuous pressurized ultrasound-assisted extraction results were reported in chapter 6. Since antioxidants are subjected to loss of activity when exposed to heat, light, and oxygen, novel and green post-processing (freeze-drying and supercritical antisolvent extraction) and microencapsulation techniques were used for antioxidant activity preservation, and to enhance product features. Thus, spray drying was employed to micro-encapsulate spent coffee grounds extracts using both inulin and maltodextrins as wall materials suitable for food application purposes. Encapsulation was optimized (chapter 4) by investigating process parameters like coating agent composition, inlet temperature, feed flow rate, using response surface methodology. In addition, different preservation techniques, finalized to prevent loss of activity and improve extract bioavailability were evaluated in chapter 5, where also a novel technique, supercritical fluid-assisted liposome formation (SuperLip), was tested for the encapsulation of the produced extracts in liposomes.

Dins el marc del projecte europeu DECISIVE (grant agreement No 689229) aquesta tesi es centra en la valorització del digestat obtingut de la gestió descentralitzada de la fracció orgànica dels residus municipals (FORM) mitjançant la tecnologia de fermentació en estat sòlid (FES). Treballs anteriors enfocats a la prova de concepte van destacar la viabilitat de produir biopesticides derivats de Bacillus thuringiensis (Bt) utilitzant digestat com a principal substrat. Partint d’;aquests resultats, es van realitzar una sèrie de dissenys d’;experiments a escala laboratori (0.5-L) per determinar els paràmetres amb més rellevància en la fermentació. La temperatura i l’;addició de FORM com a co-substrat es van identificar com a paràmetres clau del procés. Aquest efecte es va estudiar a una escala superior (1.6-L), confirmant la necessitat d’;afegir co-substrat per tal de millorar els rendiments de producció. En aquest punt, també es va identificar i destacar la importància dels nivells d’;oxigen durant les primeres hores de procés. Com a resultant, es va desenvolupar una estratègia d’;aeració per tal de maximitzar la producció d’;espores. Aquesta estratègia va ser validada a un reactor prototip (22-L), utilitzant dos soques diferents: Bt var. kurstaki i Bt var. israelensis. Els resultats van ser molt prometedors quan el procediment es realitzava en batch, però la producció final es veia reduïda significativament quan es treballava en fed-batch o batchs seqüencials. Finalment, aquesta estratègia de producció es va implementar al reactor pilot de 290-L, intentant aconseguir l’;ambient favorable per incrementar el creixement i esporulació de Bt. La qualitat del material fermentat va ser analitzada en termes de concentració d’;espores, maduresa del sòlid, i identificació i quantificació de microplàstics. Aquest projecte ha rebut finançament del programa de recerca i innovació Horizon 2020 de la Unió Europea segons el Grant Agreement No 689229.
Dentro del marco del proyecto europeo DECISIVE (grant agreement No 689229) esta tesis se centra en la valorización del digestato obtenido de la gestión descentralizada de la fracción orgánica de los residuos municipales (FORM) mediante la tecnología de fermentación en estado sólido (FES). Trabajos anteriores enfocados a la prueba de concepto destacaron la viabilidad de producir biopesticidas derivados de Bacillus thuringiensis (Bt) utilizando digestato como principal sustrato. A partir de estos resultados, se realizaron una serie de diseños de experimentos a escala laboratorio (0.5-L) con el objetivo de determinar los parámetros con más relevancia en la fermentación. La temperatura y la adición de FORM como co-sustrato se identificarion como parámetros clave del proceso. Su efecto se estudió a escala superior (1.6-L), confirmando la necesidad de añadir co-sustrato para mejorar los rendimientos de producción. En este punto, también se identificó y destacó la importancia de los niveles de oxígeno durante las primeras horas de proceso. Como resultado, se desarrolló una estrategia de aeración para maximizar la producción de esporas. Esta estrategia se validó en un reactor prototipo (22-L), utilizando dos cepas diferentes: Bt var. kurstaki y Bt var. israelensis. Los resultados fueron muy prometedores cuando el proceso operaba en bach, pero la producción final disminuía significativamente cuando se operaba en fed-batch o batch secuencial. Finalmente, esta estrategia de producción se implementó en el reactor piloto de 290-L, intentado lograr en ambiente favorable para incrementar el crecimiento y esporulación de Bt. Se estudió la calidad del sólido fermentado en referencia a la concentración de esporas, madurez del sólido, e identificación y cuantificación de microplásticos. Este proyecto ha recibido fondos del programa de investigación e innovación Horizon 2020 de la Unión Europea según el Grant Agreement No 689229.
In the framework of the European project DECISIVE (grant agreement No 689229) the present thesis is focused on the valorization of digestate from the decentralized management of the organic fraction of the municipal solid waste through the solid-state fermentation (SSF) technology. Previous work focused on the proof of concept of the idea highlighted the viability of producing Bacillus thuringiensis-derived biopesticides using digestate as a principal substrate. From these results, a first assessment at a laboratory scale (0.5-L) using the design of experiments’ methodology was performed for determining the more relevant parameters in the fermentation. Temperature and the use of biowaste as co-substrate were identified as key parameters for the process. This effect was studied at 1.6-L, confirming the need of adding co-substrate for increasing the production yields. At that point, the relevance of oxygen levels in the firsts hours of fermentation was identified and highlighted. As a result, an aeration strategy was developed with the aim of maximizing the spore production. This strategy was validated at a prototype reactor (22-L) using two different strains: Bt var. kurstaki and Bt var. israelensis. Promising results were observed when the process was performed on batch mode. However, the final production was significantly reduced when working on fed-batch or sequential batch mode. Lastly, the developed operation strategy was implemented at the 290-L pilot reactor, trying to achieve an adequate environment for boosting Bt growth and sporulation. The quality of the fermented material was assessed in terms of spore concentration, solid maturity, and microplastics identification and quantification. This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 689229.

Le monde, et en particulier l'Europe, fait face aux effets du changement climatique dus à sa longue dépendance aux combustibles fossiles en reconnaissant la nécessité vitale de s'orienter vers des ressources énergétiques renouvelables. Parmi les énergies renouvelables, la biomasse alimente non seulement la production de bioénergie, mais constitue également une source vitale de biocarbone, utilisé pour créer des molécules à haute valeur ajoutée, en remplacement des produits d'origine fossile. Les lévulinates d'alkyle, dérivés de la biomasse, se distinguent particulièrement par leur potentiel en tant que bio-additifs et biocarburants. La solvolyse acide des sucres hexagonaux de la biomasse semble être une voie de production prometteuse et rentable. Le potentiel du lévulinate d'alkyle s'étend à sa conversion en γ-valérolactone (GVL), un biosolvant prometteur, généralement obtenu par hydrogénation avec hydrogène moléculaire. En plus d'être un réactif clé, l'hydrogène est également un vecteur énergétique prometteur, facilitant l'intégration des sources d'énergie renouvelables sur le marché. Les systèmes de stockage d'énergie à base d'hydrogène soutiennent cette intégration et favorisent la transformation industrielle "verte". Cette thèse porte sur l'étude technologique et l'évaluation de la durabilité d'un système de biotransformation, intégrant la valorisation de la biomasse lignocellulosique, la production d'énergie et la génération d'hydrogène. L'étude comprend des investigations expérimentales, optimisant les technologies pour la production de lévulinate de butyle et son hydrogénation en GVL, ainsi que la simulation et l'évaluation de la durabilité de l'ensemble du procédé. Afin de répondre à la question de la durabilité, la recherche présente une première section axée sur l'étude expérimentale de la technologie optimale pour la production de lévulinate de butyle. La solvolyse de l'hexose Fructose en lévulinate de butyle a été étudiée en termes de conditions optimales de procédé et de modélisation cinétique. Sélectionné le catalyseur hétérogène, l'effet du solvant a été étudié, montrant les avantages de l'utilisation du GVL comme co-solvant, avec le butanol, sur la cinétique de conversion et de dissolution du fructose. Dans ces conditions, la solvolyse en lévulinate de butyle a été étudiée d'un point de vue cinétique, d'abord en proposant un modèle pour la solvolyse du 5-HMF, un intermédiaire dans la voie du fructose, puis en étendant la modélisation à partir du fructose lui-même. Un modèle cinétique robuste, décrivant le mécanisme réactionnel de la solvolyse, a été défini et validé, en particulier dans des conditions de concentration élevée en fructose, et en incluant dans la modélisation la cinétique de dissolution et de dégradation du fructose. Dans la deuxième partie de la recherche, la perspective technologique a été étendue à l'hydrogénation du lévulinate de butyle en GVL. À partir d'une phase de conception, le schéma global du procédé de transformation du fructose en GVL a été défini, simulé et optimisé sur la base du concept d'intensification du procédé. Le procédé a ensuite été intégré dans une étude de cas réelle en Normandie, France, en adaptant l'analyse à la disponibilité locale de la biomasse lignocellulosique et de l'énergie éolienne. L'étude définit une méthodologie pour la conception et l'intégration du système d'approvisionnement en énergie, en évaluant différents scénarios. L'évaluation de la durabilité, basée sur des indicateurs de performance couvrant les dimensions économiques, environnementales et sociales, aboutit à un indice global de durabilité. Les résultats montrent que les scénarios intégrant le système de GVL, l'énergie éolienne et le stockage de l'énergie sous forme d'hydrogène sont prometteurs, car ils démontrent une rentabilité économique élevée et un impact environnemental réduit. Enfin, des analyses de sensibilité valident la robustesse et la fiabilité de la méthodologie
The world is facing the impacts of climate change due to its long dependence on fossil fuels, and specifically Europe, which is facing an energy crisis, has recognized the fragility of its fossil fuel-dependent energy system and has moved strongly towards renewable energy resources. Among renewables, biomass not only powers bio-energy production but also serves as a vital source of bio-carbon, used to create high-value molecules, replacing fossil-based products. Alkyl levulinates, derived from biomass, particularly stand out for their potential as bio-additives and bio-fuels. Acid solvolysis of hexose sugars from biomass appears to be a promising and cost-effective production route, which requires further investigation not yet found in the literature. The potential of alkyl levulinate extends to its conversion into γ-valerolactone (GVL), a promising bio-solvent, commonly obtained by hydrogenation through molecular-hydrogen. Besides being a key reagent, hydrogen is also a promising energy carrier, facilitating the integration of renewable energy sources into the market. Hydrogen energy storage systems support this integration, promoting 'green' industrial transformation. This thesis focuses on technological investigation and sustainability assessment of a potential biorefinery system, integrating lignocellulosic biomass valorization, energy production, and hydrogen generation. The study encompasses experimental investigations, optimizing technologies for the production of butyl levulinate and its subsequent hydrogenation to GVL. Sustainability considerations are fundamental to the process configuration, aligning with the global shift towards renewable and carbon bio-resources. In order to answer the question of sustainability, the research presents a first section focused on the experimental investigation of the optimal technology for the production of butyl levulinate. The solvolysis of the biomass-derived hexose Fructose to butyl levulinate was investigated, in terms of optimal process conditions and kinetic modelling. Selected an effective heterogeneous catalyst, the effect of the solvent was investigated, showing the benefits of using GVL as co-solvent, together with butanol, on the conversion and dissolution kinetics of fructose. In these conditions, the solvolysis to butyl levulinate was studied in depth from a kinetic point of view, first by proposing a model for the solvolysis of 5-HMF, an intermediate in the fructose pathway, and then extending the modelling from fructose itself. A robust kinetic model, describing the reaction mechanism of solvolysis, was defined and validated, particularly under conditions of high initial fructose concentration (applying the concept of High-gravity), and including in the modelling the kinetics of dissolution, and degradation of fructose, under acidic conditions.In the second part of the research, the technological perspective was extended to the hydrogenation of butyl levulinate to GVL. Starting from a conceptual design phase, the overall fructose-to-GVL process scheme was defined, simulated, and optimized on the basis of the process intensification concept. In the third part, the process was then dropped into a real case study in Normandy, France, adapting the analysis to the local availability of lignocellulosic biomass and wind energy. The study defines a methodology for designing and integrating the energy-supply system, evaluating different scenarios. The sustainability assessment, based on key performance indicators spanning economic, environmental, and social dimensions, culminates in an aggregated overall sustainability index. The results highlight scenarios integrating the GVL biorefinery system with wind power and hydrogen energy storage as promising, demonstrating high economic profitability and reduced environmental impact. Finally, sensitivity analyses validate the robustness and reliability of the methodology, generally extendable also to other technological systems
Come previsto, il mondo sta affrontando gli effetti tangibili del cambiamento climatico come conseguenza di un'economia basata sui combustibili fossili per centinaia di anni. Oltre a dover affrontare e adottare misure correttive per limitare gli effetti del riscaldamento globale, l'Europa sta affrontando una grave crisi energetica, che rivela la fragilità del sistema energetico europeo, prevalentemente dipendente dalle importazioni di combustibili fossili. La geopolitica delle risorse fossili ha innescato la necessaria rimodulazione dell'economia energetica europea, che si sta spostando "forzatamente" verso le risorse energetiche rinnovabili per diventare un'economia fossile e a zero emissioni di carbonio. Nel panorama delle rinnovabili, le risorse più sfruttate sono l'energia solare, eolica e da biomassa. Oltre alla produzione di bioenergia, la biomassa è una fonte inestimabile di biocarbonio, che può essere sfruttata e valorizzata per la produzione di molecole ad alto valore aggiunto che possono essere utilizzate in vari settori industriali, per la produzione di carburanti, prodotti chimici, materiali e sostituendo i corrispondenti prodotti di origine fossile. In questo contesto, sono stati sviluppati sistemi innovativi di bioraffinazione della biomassa di seconda generazione per trasformare e decostruire la complessa struttura della biomassa in molecole piattaforma più semplici, che possono poi essere trasformate in molecole ad alto potenziale. Tra queste, gli alchil levulinati sono stati identificati per il loro notevole potenziale come bioadditivi e biocarburanti. Esteri dell'acido levulinico, questi composti possono essere ottenuti da derivati della biomassa, come i monosaccaridi dello zucchero, secondo diverse vie di reazione; tra queste, la solvolisi acida degli zuccheri esosi può essere una via di produzione promettente ed economicamente vantaggiosa, che richiede ulteriori indagini non ancora presenti in letteratura. Il potenziale degli alchil levulinati risiede anche nella possibilità di un ulteriore trasformazione mediante idrogenazione per produrre γ-valerolattone (GVL), una molecola con un mercato promettente come bio-solvente, grazie alle sue proprietà di stabilità, ecotossicità e biodegradabilità. L'uso dell'idrogeno gassoso è la via più comune per l'idrogenazione del GVL, ma, oltre a essere un reagente chimico fondamentale, l'idrogeno è anche uno dei principali protagonisti della transizione energetica. Infatti, come vettore energetico, l'idrogeno può portare alla piena penetrazione delle fonti energetiche rinnovabili nel mercato dell'energia, costituendo un complemento-tampone per lo stoccaggio delle energie rinnovabili intermittenti, attraverso la progettazione di sistemi di stoccaggio dell'energia dell'idrogeno (HydESS). L'accumulo di energia a idrogeno a lungo termine può consentire l'autosufficienza dei sistemi di energia rinnovabile, in quanto agisce da ponte tra le funzionalità dei sistemi Power-to-Hydrogen, in grado di assorbire i surplus energetici delle energie rinnovabili e di immagazzinarli, e quelle dei sistemi Hydrogen-to-Power, che restituiscono energia rinnovabile quando le fonti di energia primaria non sono disponibili. In quest'ottica, lo sviluppo di tali sistemi può portare all'integrazione completa e stabile delle fonti di energia rinnovabile in asset industriali già esistenti, così come in nuovi mercati industriali, come le bioraffinerie di biomassa lignocellulosica, promuovendo lo sviluppo di realtà industriali "verdi" in termini di trasformazione di materiali ed energia. Il mercato industriale globale si sta evolvendo verso la decarbonizzazione e la riqualificazione di diversi asset, attraverso investimenti in efficienza energetica e l'introduzione di processi green per la valorizzazione delle fonti rinnovabili, ma l'implementazione su larga scala di queste iniziative richiede un'analisi completa e approfondita della loro sostenibilità

En la industria de la construcción es usual que los contratistas busquen contar con subcontratistas con el fin de asegurar la calidad de los trabajos de mayor especialización como acabados, equipamiento, etc. Sin embargo, esto genera que se incremente la supervisión y control de estos trabajos. A partir del análisis de 04 proyectos de edificaciones multifamiliares, se detectó que existe una deficiencia en el proceso de valorización de los subcontratistas de acabados. La investigación desarrolla una propuesta de optimización de este proceso, basada en la herramienta Dynamo dentro de un entorno de trabajo BIM. Los resultados muestran una comparación en el tiempo del método tradicional de valorización y el método propuesto, obteniendo una reducción de tiempo de 27.5%. Asimismo, se señala los principales beneficios de la propuesta, los cuales se agrupan en control del proyecto, alcance de los subcontratistas, visualización del avance, tiempo y costo.
In the construction industry, it is common for contractors to seek subcontractors in order to ensure the quality of specialized jobs such as finishes, equipment, etc. However, this leads to increased supervision and control of these jobs. From the analysis of 04 multi-family building projects, it was detected that there is a deficiency in the subcontractor’s schedule of values of finishes process. This research develops a proposal to optimize this process, based on the software Dynamo within a Building Information Modelling (BIM) work environment. The results showed a comparison in time between the traditional method and the proposed method, obtaining a time reduction of 27.5%. Furthermore, the main benefits of the proposal are indicated, which are grouped into project control, scope of subcontractors, progress tracking, time and cost.
Trabajo de investigación

La forte augmentation de la population mondiale entraîne une demande croissante en eau potable. La production d'eau potable est accompagnée par la génération de résidus du traitement de l'eau dont la boue d'aluminium qui est donc largement disponible mondialement. Ce travail se concentre sur l'identification des différentes voies de valorisation des boues d'aluminium afin de les réutiliser dans le domaine de l’environnement. Deux sources de boues d'aluminium, collectées en France et en Irlande, ont été étudiées dans divers domaines d’application en fonction de leurs caractéristiques. Tout d'abord, les boues d'aluminium ont été utilisées en remplacement d’une partie de l'argile dans la fabrication des briques, en incorporant différents pourcentages de boues d'aluminium et à différentes températures. Les briques résultantes ont été caractérisées et les résultats ont montré que les briques composées de boues d'aluminium et d'argile sont conformes aux « normes européennes et irlandaises » et démontrent ainsi le potentiel pour une application industrielle des boues d'aluminium dans la fabrication de briques en terre cuite irlandaises. Dans un second temps, les boues d’aluminium ont été utilisées comme adsorbant des polluants présents dans l’agriculture. Le glyphosate est un ingrédient actif dans les pesticides utilisés massivement dans l'agriculture irlandaise et représente une problématique environnementale. La boue d’aluminium et la tourbe irlandaise ont été comparées pour l’élimination du glyphosate lors de tests en pot à l’échelle laboratoire. Les résultats ont montré que la boue d’aluminium permet d’éliminer le glyphosate à plus de 99% et réduire les niveaux de DCO. Cet aspect scientifique a permis d’être dans la sélection des adsorbants possibles pour le traitement des eaux usées agricoles en Irlande. Le co-conditionnement et la déshydratation des boues de station d’épuration avec des boues d’aluminium liquides ont également été étudiés. Pour cela, le Jar test a été effectué sur des boues issues d’une station de traitement des eaux française. Les résultats ont montré que le rapport optimal de mélange des boues est de 1:1 (boues d’épuration : boues d’aluminium). Ainsi, la quantité de polymère utilisée peut être diminuée de 14 fois par rapport aux technologies actuelles. Cette approche a permis de montrer la possible valorisation des boues d’aluminium comme un moyen durable et technique permettant ainsi l’élimination des boues localement pour une même station de traitement des eaux. Une autre voie de valorisation des boues d’aluminium comme adsorbant pour la purification des gaz a été étudiée lors d’expériences d’adsorption de H2S dans un réacteur à lit fixe dans différentes conditions expérimentales. Les données expérimentales d’adsorption du H2S ont été modélisées à l'aide de modèles empiriques basés sur la cinétique des processus d'adsorption. Les résultats ont montré que les boues d'aluminium sont un adsorbant efficace pour l'élimination du H2S (capacité de 374,2 mg H2S / g solide) et que des mécanismes mis en jeu sont l'adsorption dissociative et l'oxydation. Les coefficients de transfert de masse globaux ont également été calculés et pouvant ainsi être utilisés pour la prédiction. Enfin, les gâteaux de boues d'aluminium ont été réutilisés pour la purification simultanée d’H2S et le traitement des eaux usées. Les résultats ont montré la capacité de cet adsorbant pour éliminer tout le H2S présent avec une grande efficacité d’élimination de la DCO, TN et TP. Ainsi, il a été démontré la valorisation des boues d’aluminium en tant qu’adsorbant pour une purification du H2S simultanée avec le traitement des eaux usées
The production of drinking water always accompanied by the generation of water treatment residues (WTRs). Alum sludge is one of the WTRs, it is an easily, locally and largely available by-product worldwide. This work focuses on the identification of different ways to valorize the alum sludge for environmentally friendly reuse. Two alum sludges collected from France and Ireland have been reused in various fields as a function of their characteristics. Firstly, alum sludge was used as a partial replacement for clay in brick making, by incorporating different percentages of alum sludge and calcined at different temperatures (range from 800 to 1200 °C). The resultant bricks were tested for compression, Loss on Ignition, water absorption, appearance, etc. Results show that alum sludge-clay bricks have met the “European and Irish Standards” and demonstrated the huge industrial application potential for alum sludge in Irish clay brick manufacturing. Glyphosate is an active ingredient in pesticide which is massive employed in agriculture. Alum sludge and Irish peat were compared for glyphosate removal in pot tests, results show that alum sludge present significant glyphosate removal capacity (>99 %) and could reduce the level of Chemical Oxygen Demand (COD). It provided a scientific clue for sorbents selection when considering the agricultural wastewater treatment in Ireland and to maximize their value in practice. The co-conditioning and dewatering of sewerage sludge with liquid alum sludge was also investigated in Jar-test based on the case analysis of a water industry in France. Results show that the optimal sludge mix ratio is 1:1, the use of the alum sludge has been shown to beneficially enhance the dewaterability of the resultant mixed sludge, and highlighting a huge polymer saving (14 times less than the current technologies) and provided a sustainable and technical sludge disposal route for the local water industry. The use of alum sludge as a sorbent for gas purification was studied by H2S adsorption experiments in a fixed-bed reactor with various operating parameters. The experimental breakthrough data were modeled with empirical models based on adsorption kinetics. Results show that alum sludge is an efficient sorbent for H2S removal (capacity of 374.2 mg/g) and the mechanisms including dissociative adsorption and oxidation were proposed. Moreover, the overall mass transfer coefficients were calculated which could be used for the process scaling up. Finally, alum sludge cakes were reused in the novel aerated alum sludge constructed wetland (CW), which were designed for simultaneous H2S purification and wastewater treatment. Results show that H2S was completely removed in the six months’ trials, while the high removal efficiencies of COD, total nitrogen (TN), total phosphates (TP) were achieved. Thus, a novel eco-friendly CW for simultaneous H2S purification and wastewater treatment was developed. In the different approaches and process considered, in particular it was put in investigating and describing the mechanisms involved. Overall, this work demonstrated alum sludge could be a promising by- product for various novel beneficial reuse rather than landfilling and provided a “Circular Economy” approach for WTRs management

This study aim at the valorization of wine industry by products; particularly on the extraction and characterization of grape seeds oil using supercritical CO2 (SC-CO2) and polyphenols from grape skins and defatted grape seeds using subcritical water (SW) and then, modeling of the kinetics of extractions and process economic analysis. The overall objective of the work is to develop recovery strategies for wine-making wastes in order to reduce their environmental impact and to valorize them in order to provide wine-makers with the possibility of selling by-products at a profitable price. To address the objectives, the work is divided into seven Chapters. In Chapter 1, some general overview and the fundamental of SC-CO2 and SW technologies along with emerging areas of applications are presented. Special emphasis is given to the work in the field of valorization of agro-industrial by-products. Then, the Chapter ends by stating the general and specific objectives of the thesis. The second Chapter is devoted to the characterization of grape seeds oil. To make the result more holistic, grape seeds from six grape cultivars were extracted using SC-CO2 in two subsequent harvesting years and the resulting oils were characterized. Comparative extractions were also performed by utilizing conventional solvent extraction using n-hexane and by mechanical press. The results testify the potentiality of grape seed oil as a source of unsaturated fatty acids and tocols. Moreover, they offers a clear picture of the similarities and differences among oils from different grape cultivars and obtained through different extraction techniques. The third Chapter is dedicated to compare the effectiveness of the models used to evaluate the kinetic of SC-CO2 extraction curves. Particularly, three models, the broken and intact cells (BIC), the shrinking core (SC), and the bridge (combined BIC-SC) models are critically analyzed. The objective of the Chapter is to objectively choose the best model that can be used in the subsequent Chapters. In order to model the kinetics of SC-CO2 extraction, one of the very important parameter is the solute solubility. But solubility data (especially of grape seed oil) is very scares in the literature. The bulk majority of the scientific works estimate the value of solubility of solute in SC-CO2 from theoretical models. So, the fourth Chapter is devoted to experimental determination of solubility of grape seed oil in SC-CO2 over a range of pressure and temperature of practical importance and the data were modeled by different models to compare their effectiveness. The fifth Chapter is aimed to study the effect of the main process variables affecting the SC-CO2 extraction of oil from grape seeds, both experimentally and through modeling. The dependency of the extraction kinetics on the variables more tested in the literature (pressure, temperature, particle size and solvent flow rate) was confirmed, and original trends were obtained for the less investigated variables, such as the bed porosity (ε), the extractor diameter to length ratio (D/L), the extractor free volume and the type of cultivars. In the sixth Chapter the attention is moved to the valorization of grape skins and defatted grape seeds by using SW. The results show that, both skins and defatted seeds contain significant concentration of polyphenols and SW is a potential green solvent for extracting valuable polyphenols from wine-making by-products. The extraction kinetics was also simulated by a simple model available in the literature. In the seventh and last Chapter, a preliminary economic feasibility study was investigated for the establishment of SC-CO2 extraction plant for the extraction of grape seeds oil. The result shows that, a SC-CO2 extraction plant is technically viable and economically feasible for the extraction of grape seed oil with estimated rate of return on investment at 8.5% and payback period of 5 year at current minimum retail selling price of grape seed oil in the market. The project has an attractive socio-economic and environmental benefit and generates substantial revenue for the local government in the form of tax and will allow wine-makers to sell wet grape marc at a price of up to US$ 10/ton.

This study aim at the valorization of wine industry by products; particularly on the extraction and characterization of grape seeds oil using supercritical CO2 (SC-CO2) and polyphenols from grape skins and defatted grape seeds using subcritical water (SW) and then, modeling of the kinetics of extractions and process economic analysis. The overall objective of the work is to develop recovery strategies for wine-making wastes in order to reduce their environmental impact and to valorize them in order to provide wine-makers with the possibility of selling by-products at a profitable price. To address the objectives, the work is divided into seven Chapters. In Chapter 1, some general overview and the fundamental of SC-CO2 and SW technologies along with emerging areas of applications are presented. Special emphasis is given to the work in the field of valorization of agro-industrial by-products. Then, the Chapter ends by stating the general and specific objectives of the thesis. The second Chapter is devoted to the characterization of grape seeds oil. To make the result more holistic, grape seeds from six grape cultivars were extracted using SC-CO2 in two subsequent harvesting years and the resulting oils were characterized. Comparative extractions were also performed by utilizing conventional solvent extraction using n-hexane and by mechanical press. The results testify the potentiality of grape seed oil as a source of unsaturated fatty acids and tocols. Moreover, they offers a clear picture of the similarities and differences among oils from different grape cultivars and obtained through different extraction techniques. The third Chapter is dedicated to compare the effectiveness of the models used to evaluate the kinetic of SC-CO2 extraction curves. Particularly, three models, the broken and intact cells (BIC), the shrinking core (SC), and the bridge (combined BIC-SC) models are critically analyzed. The objective of the Chapter is to objectively choose the best model that can be used in the subsequent Chapters. In order to model the kinetics of SC-CO2 extraction, one of the very important parameter is the solute solubility. But solubility data (especially of grape seed oil) is very scares in the literature. The bulk majority of the scientific works estimate the value of solubility of solute in SC-CO2 from theoretical models. So, the fourth Chapter is devoted to experimental determination of solubility of grape seed oil in SC-CO2 over a range of pressure and temperature of practical importance and the data were modeled by different models to compare their effectiveness. The fifth Chapter is aimed to study the effect of the main process variables affecting the SC-CO2 extraction of oil from grape seeds, both experimentally and through modeling. The dependency of the extraction kinetics on the variables more tested in the literature (pressure, temperature, particle size and solvent flow rate) was confirmed, and original trends were obtained for the less investigated variables, such as the bed porosity (ε), the extractor diameter to length ratio (D/L), the extractor free volume and the type of cultivars. In the sixth Chapter the attention is moved to the valorization of grape skins and defatted grape seeds by using SW. The results show that, both skins and defatted seeds contain significant concentration of polyphenols and SW is a potential green solvent for extracting valuable polyphenols from wine-making by-products. The extraction kinetics was also simulated by a simple model available in the literature. In the seventh and last Chapter, a preliminary economic feasibility study was investigated for the establishment of SC-CO2 extraction plant for the extraction of grape seeds oil. The result shows that, a SC-CO2 extraction plant is technically viable and economically feasible for the extraction of grape seed oil with estimated rate of return on investment at 8.5% and payback period of 5 year at current minimum retail selling price of grape seed oil in the market. The project has an attractive socio-economic and environmental benefit and generates substantial revenue for the local government in the form of tax and will allow wine-makers to sell wet grape marc at a price of up to US$ 10/ton.

Food wastage represents a massive issue in today's society. It impacts the environment (e.g., climate change, resources depletion, biodiversity loss), society (e.g. food security), and the global economy. All the stakeholders could change systemically to transition towards the circular economy. Corporates must involve leadership, employees, suppliers, and consumers to build a more efficient and resilient system where waste and by-products generation is limited. The unavoidable waste could be valorized to new raw materials to reduce the environmental impact of their disposal. This thesis focuses on Barilla (the Italian food company since 1877) and its willingness to valorize by-products (e.g. bread crust), maximizing all aspects of sustainability: economy, ecology, and social equity. First, the author formed an Upcycling Team, an inter-functional group of voluntaries, to define Barilla's criteria for by-products valorization. Afterwards, the Team screened the possible bread crust valorization options (e.g. food product, beer, and animal feed production) using the Analytic Hierarchy Process (AHP), a decision-making tool that allows selecting the best alternative under conflicting criteria. The method's strength is the ability to judge the elements in pairs and use qualitative evaluation. The AHP suggested that producing a food product (e.g. rusk) is the most sustainable option. Furthermore, the author carried out a partial Life Cycle Assessment to compare the global warming potential (GWP) of the production of upcycled rusk to animal feed accounting for the avoided production of the standard products. She demonstrated that producing upcycled rusks using 1 kg of bread crust results in greater net-reduction of GHG emissions than upcycled animal feed. These findings may push Barilla to implement an upcycled food product designed by adopting the eco-design approach to implement a sustainable food product from its raw materials to its end-of-life.

Orientador: Zacarias Pereira Borges
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Educação
Made available in DSpace on 2018-08-05T20:41:14Z (GMT). No. of bitstreams: 1 Lucio_Roque_M.pdf: 950689 bytes, checksum: 08c819ed7acbd4f88501f73bd78c5d93 (MD5) Previous issue date: 2005
Resumo: Esta pesquisa enfoca a implementação da municipalização do ensino em quatro municípios da região de São João da Boa Vista (SP) de 1997 e 2003: Mococa, São José do Rio Pardo, São Sebastião da Grama e Tapiratiba. Procurou-se entender: Por que quatro municípios do estado de São Paulo tomaram diferentes caminhos na implementação de uma mesma política educacional? O trabalho teve como objetivos: analisar a implementação da municipalização do ensino nos quatro municípios tendo em vista a utilização dos recursos financeiros do FUNDEF; investigar se houve melhoria no processo ensino ¿ aprendizagem, tomando como ponto de partida a municipalização do ensino, identificar os fatores positivos e apontar insuficiências e equívocos, buscando o aperfeiçoamento ou reformulação desta política educacional e oferecer subsídios à ação de Dirigentes Municipais de Educação, para continuidade ou mudanças de rumo nesta política educacional. Tratou-se, portanto, de pesquisa qualitativa, utilizando-se como referencial teórico a Análise de Política e tendo como procedimentos a análise de documentos legais dos municípios estudados, do estado de São Paulo e do Brasil, bem como de dados estatísticos, entrevistas e questionários semi-estruturados. Apresentou-se, como pano de fundo, a política educacional brasileira, enfocando a condição do Município na Federação, a autonomia dos municípios, as políticas de descentralização do século XIX à Constituição Federal de 1988 e à sua emenda indutora da municipalização do ensino. Apresentaram-se os perfis dos municípios envolvidos: fundação, contexto atual, municipalização do ensino, análise dos recursos financeiros recebidos no período e a implementação da municipalização. Comparam-se, em seguida os processos de municipalização do ensino nos quatro municípios, desvelando-se suas diferenças e similitudes. Por fim, estabeleceu-se um contraponto com alguns estudos da temática e um balanço da consecução dos objetivos e apontam-se algumas conclusões, com a indicação de ações pertinentes ao processo de municipalização em andamento
Abstract: This search brings to a focus the settlement of municipal autonomic upbringing systems in four towns in the region of São João da Boa Vista from 1997 to 2003: Mococa, São José do Rio Pardo, São Sebastião da Grama and Tapiratiba.It was tried to understand why four towns in São Paulo upstate carried out in different ways the same upbringing policy. The purposes of this work have been: analysis of how municipal autonomic upbringing systems have been performed in four towns as to the usage of FUNDEF pecuniary resources; inquiry about municipal autonomic upbringing system to find out whether there was improvement in process of teaching and apprenticeship or not, as a result of the municipal autonomic upbringing system settlement, and at the same time to identify positive elements and to point out faults, shortages and mistakes in order to better or to plan out again such an upbringing policy and finally to offer subsidies for municipal upbringing active leaders to perform their work so that the adopted upbringing policies may go or be changed. This work intends to be a quality search as it uses the political inquiry as a theoretical remark and the examination of town hall legal documents as procedure ¿ just those from thes towns in São Paulo upstate and from other towns in Brazil which have been studied here; statistical data, interviews and half-structured questionaries. As a background, the brazilian national education policy appears bringing to a focus the condition of the municipal district in federacy, the self-government of municipal districts, the decentralizing policies in the nineteenth century up till the national constitution in 1988 and its amendment inducing to settlement of municipal autonomic upbringing system. The following profiles of the municipal districts that brought forth their own upbringing systems come to mind: foudation, today¿s context, settlement of municipal autonomic upbringing system, examination of pecuniary resources cashed in for that purpose and the accomplishment of municipal upbringing plan. Afterwards, the four types of municipal autonomic upbringing system (in the four municipal districts here mentioned) are compared with each other and differences and likenesses (similiarities) are revealed. Finally, a couterpoint is set up towards some studies about the theme as well as a ponderation about ends gained. Some illations are brought forward and actions pertaining to the municipal autonomic upbringing system newly settled are pointed out
Mestrado
Politicas de Educação e Sistemas Educativos
Mestre em Educação

Development of new biocomposites made with biopolymeric matrixes and biofillers coming from nut shells particles. Evaluation of how these fillers may change the thermal and mechanical properties of the material by changing the type of shell, grain size and quantity. The main properties analysed are: - Wettability of the powders - Melting and glass transition temperature - Degree of crystallinity - Young Modulus - Stress at maximum load and at break - Elongation at maximum load and at break - Hardness - Impact Resistance Finally it is presented a possible application of these new materials in packaging.

L’entreprise PAVATEX appartenant au groupe SOPREMA, spécialisée dans la production de panneaux isolants à base de fibres de bois, souhaite étudier, dans le cadre du projet SoPRANo’TEX, l'élargissement de ses sources d'approvisionnement à d'autres essences de bois moins onéreuses. De plus, afin de participer activement au développement de la filière de valorisation des déchets issus de la filière ameublement (DEA), l'intégration de déchets bois fait partie des objectifs du projet. Ces déchets contiennent une part significative d'adjuvants, notamment de colle urée-formaldéhyde, qu'il convient d'éliminer pour rendre plus simple l’introduction de ce type de déchet en tant que matière première dans les industries de la filière bois. C'est pourquoi une étape de traitement thermique est envisagée pour les DEA, d'une part pour "dépolluer" la matière première et aussi pour conférer au matériau des propriétés particulières notamment par abaissement de son caractère hygroscopique. Les résultats attendus étant un abaissement des consommations énergétiques de l'étape de défibrage, une limitation du transfert de polluants vers les effluents gazeux et liquides de l'étape de défibrage et une amélioration des propriétés du matériau final, notamment concernant sa stabilité dimensionnelle, sa durabilité vis à vis des champignons et ses performances thermiques en conditions humides. Une seconde voie de dépollution des déchets, l’hydrothermolyse (ou cuisson à la vapeur), a été identifiée au cours de la thèse. En effet, Les résines contenues dans les DEA s’hydrolysent facilement, ce qui permet de dépolluer efficacement la matière en limitant la dégradation du bois.Le travail de thèse porte principalement sur les étapes de traitement thermique, de défibrage et d’hydrothermolyse avec pour objectifs de caractériser les effluents liquides et gazeux à chaque étape. Le but de ces travaux est également d'optimiser les conditions opératoires de ces procédés afin produire des DEA traités thermiquement, en quantités conséquentes (échelle pilote), pour ensuite élaborer des fibres adaptées à la fabrication de panneaux isolants en fibres de bois. La dernière phase du travail de thèse consiste en la fabrication et en la caractérisation des performances des panneaux isolants en fibres de bois prototypes réalisés et de déterminer l’incidence des différentes variables. Une étude technico-économique est également proposée à partir de l’état de l’art et des données expérimentales selon différents scénarios pour évaluer l’intérêt des voies proposées
The PAVATEX company, which belongs to SOPREMA group is a manufacturer of insulating wood fiber panels, is interested in expanding its supply sources to other less expensive wood species within the SoPRANo'TEX project. In addition, in order to contribute actively to the development of the furniture wood waste recycling industry, the introduction of wood waste is part of the project's goals. These wastes contain a significant part of additives, in particular urea-formaldehyde glue, which it is convenient to remove to improve the use of this type of waste as raw material in the timber industry.This is why a thermal treatment stage is envisaged for the wood wastes, on the one hand to " clean " the matter and also to confer to the wood some specific properties by reducing its hygroscopic character. The outcomes expected are a reduction of the energy consumption of the defibration stage, a limitation of the transfer of pollutants to the gaseous and liquid effluents of the defibering stage and an improvement of the final material properties, in particular concerning its dimensional stability, its durability against fungi and its thermal performances in wet conditions. A second way of waste depollution, hydrothermolysis (or steam cooking), has been identified during the thesis. Indeed, the resins contained in the DEA are easily hydrolyzed, which allows to decontaminate efficiently the material while limiting the degradation of the wood.The thesis focuses on the thermal treatment, defibering and hydrothermolysis processes with the objective of analyzing the liquid and gaseous effluents for each process. The aim of this work is also to optimize the operating conditions of these processes in order to produce thermally treated wood wastes, in large quantities (pilot scale), in order to elaborate fibers adapted to the manufacture of wood fiber insulating panels. The last phase of the thesis work consists in the manufacturing and in the performance characterization of panels prototypes manufactured and to determine the impact of various parameters. A technico-economic study is also proposed from the state of the art and experimental data according to the proposed scenarios to evaluate the interest of these ways

O presente trabalho objetiva estudar sobretudo a valorização dos precedentes no processo civil brasileiro, com especial atenção para os mecanismos indutores da criação de precedentes, observando se há benefícios para a efetividade da tutela jurisdicional. São traçados breves contornos do que constitui um precedente judicial, da ratio decidendi e dos obiter dicta, dos precedentes verticais e horizontais, bem como da classificação das normas segunda sua abstração e generalidade e, por fim, da teoria econômica dos precedentes. Depois, se estudam os principais mecanismos de valorização dos precedentes encontrados no processo civil brasileiro vigente, sobretudo no Código de Processo Civil de 1973 (CPC-73). A seguir, a valorização dos precedentes é estudada do ponto de vista dos conflitos repetitivos, a relação entre demandas que veiculam questões repetitivas, e como isso afeta a indução da criação de precedentes. Ao final, estuda-se com maior atenção o incidente de resolução de demandas repetitivas, previsto no Anteprojeto de Novo Código de Processo Civil, sua origem, institutos similares de outros países e, ainda, eventuais dificuldades ou sugestões de alteração indicadas pelo direito comparado. Conclui-se o trabalho, então, tecendo-se alguns comentários a respeito de como as técnicas de valorização dos precedentes, que induzem a criação de precedentes (como o incidente estudado) poderiam melhor atender ao fim colimado, que é a efetividade da tutela jurisdicional
This work aims mainly at the study of the valorization of precedents in Brazilian civil procedure, with special attention to the precedent creation mechanisms, observing if there are benefits for a more effective adjudication (in lieu of the scopes of the jurisdiction). We streamline the main contours of a judicial precedent, its ratio decidendi and obiter dictum, the vertical and horizontal precedents, as well as the classifcation of legal rules according to their abstraction and generality and, at last, the economical theory of precedents. Then, we study the main mechanisms of valorizing precedents in Brazilian civil procedure in force, especially in the Civil Procedure Code of 1973 (CPC-73). Following that line of thought, the valorization of precedents is seen from the viewpoint of the repetitive litigation, the relation between repetitive lawsuits, and then how it afects the inducement of precedent creation. Afterwards, the attention is focused on the to-be-created incident of resolution of repetitive lawsuits (as of the Draft of New Brazilian Civil Procedure Code), its origins, similar mechanisms of other countries, and possible difficulties or recommendations inspired by the foreign law for amendment of the draft. Lastly, the work is closed by shedding some light on how the techniques for valorization of precedents could better serve the aim collimated, which is the effectiveness of jurisdictional protection.

The present work aims at the evaluation of the possibility to use different organic wastes, as substrates for the production of hexanoic acid and methane, through anaerobic fermentation process. The substrates that will be examined are red and white grape pomaces, for the production of volatile fatty acids, and different agro-industrial waste, coming from insects breeding, for the production of biomethane. The first goal is the establishment of an appropriate culture medium, for the acidogenesis and chain elongation processes, in order to achieve a high concentration of hexanoic acid in the fermentation broth. The culture medium is mostly composed by ethanol, acetic acid and sodium hydrogen carbonate: ethanol is used as the electron donor of the chain elongation process; acetic acid is the source of organic carbon; sodium hydrogen carbonate is the alkalinity regulator. The essay’s results show that each of them is mandatory inside the fermentation broth, with a specific concentration and molar ratio. The study of the production of hexanoic acid was conducted in batch reactors, using red or white grape pomaces. The concentrations of VFAs achieved through the batch culture were high, allowing an easy recovery of them from the fermentation broth. The yield of the process, using red grape pomace, was higher than the yield of white grape pomace. A pseudo-continuous process was set up, in order to monitor its performance with respect to the batch process. The results showed lower concentrations achieved with the last process, with respect to the batch one. The biochemical methane potential study of different agro-industrial residues was carried out: each substrate produced a certain amount of methane, demonstrating the possibility to use them as feeding for an industrial anaerobic digestor. The methane yields found were lower than the average of methane yield of fresh organic waste.

L'épuisement des ressources et l'accumulation des gaz polluants dans l'atmosphère suscitent aujourd'hui des inquiétudes grandissantes. La transition énergétique en cours nécessite que certains procédés de transformation de la matière et de l'énergie soient partiellement modifiés ou profondément repensés pour s'adapter à des conditions de fonctionnement plus durables. L'électricité et l'hydrogène bas carbone peuvent se substituer aux énergies fossiles conduisant ainsi à un mix énergétique dont l'empreinte Gaz à Effet de Serre (GES) est faible. Outre l'hydrogène, la production de carburants alternatifs et des produits à forte valeur ajoutée est une autre piste pour accompagner la transition énergétique. La recherche de procédés optimaux, durables et économiques est donc un défi majeur auquel les ingénieurs procédés sont confrontés. Le présent travail s'est ainsi focalisé sur l'intensification des procédés de transformation de la matière et de l'énergie, au travers d'unités multifonctionnelles qui exploitent les synergies entre fonctions élémentaires de transformation (réaction, transfert, séparation, etc.) au sein d'un équipement intensif. La notion de réacteurs multifonctionnels, couplant plusieurs fonctions élémentaires, a connu un réel succès d'estime lorsque des démonstrateurs historiques ont vu le jour (procédé Eastman-Kodak, etc.), mais leur implémentation ne s'est pas généralisée par manque de méthodologie de conception pratique. Ce travail porte sur l'application de certaines méthodologies d'intensification pour la compréhension et l'amélioration des performances d'un procédé mettant œuvre des réactions exothermiques équilibrées. La synthèse directe du diméthyl éther (DME) à partir de CO₂ et d'H₂ est retenue comme cas d'étude. Différentes voies exploratoires de développement du procédé de synthèse directe du DME ont été étudiées en s'appuyant sur la modélisation et la simulation. Le réacteur-échangeur de chaleur, le réacteur multifonctionnel (réacteur-échangeur de chaleur-séparateur membranaire), les procédés hybrides de briques élémentaires et un procédé plaçant le réacteur refroidi dans un environnement de procédé classique en présence d'autres opérations unitaires et de recyclages, sont étudiées sous différents angles. Différents cas et stratégies d'optimisation ont été traités qui se distinguent par les variables de décision et la méthode de résolution. Les différentes méthodologies appliquées ont permis de démontrer leur pertinence en termes de solutions obtenues et d'ouverture vers l'innovation des procédés. A l'échelle de l'équipement, l'optimisation des profils représente le cœur de la méthodologie. Les résultats mettent en évidence le potentiel des réacteurs multifonctionnels : une conversion de CO₂ par passe de l'ordre de 98%, un rendement en DME de l'ordre de 95% et une possibilité d'élimination d'une colonne de distillation sont obtenus. Dans le but d'évaluer les caractéristiques du maximum atteignable dans un réacteur multifonctionnel, un procédé hybride de briques élémentaires a été optimisé. A l'échelle du procédé, le comportement du réacteur a été étudié pour comprendre l'impact de l'intégration du réacteur dans une boucle de recyclage et estimer les effets locaux et globaux sur les multiples critères de performances. Sur la base de critères de rendement global en DME, de conversion globale de CO₂, de TRL, etc., la comparaison des différents designs a montré qu'une réduction du nombre d'équipements d'un facteur 11 est possible dans le cas du choix d'un réacteur multifonctionnel
The depletion of resources and the accumulation of pollutant gases in the atmosphere are nowadays of growing concern. The current energy transition requires that certain material and energy transformation processes be partially modified or profoundly reconsidered to fit more sustainable operating conditions. Low-carbon electricity and hydrogen can substitute fossil fuels, leading to an energy mix with a low greenhouse gas (GHG) footprint. In addition to hydrogen, the production of alternative fuels and high value-added products is another way to support the energy transition.Looking for optimal, sustainable and economical processes is therefore a major challenge that process engineers are facing. The present work has thus focused on the intensification of mass and energy transformation processes, through multifunctional units, which take advantage of the synergies between elementary functions of transformation (reaction, transfer, separation, etc.) within an intensive equipment. The concept of multifunctional reactors, coupling several elementary functions, has been a real success when historical demonstrators were created (Eastman-Kodak process, etc.), but their implementation has not been generalized, due to a lack of practical design methodology.This work focuses on the implementation of some intensification methodologies to understand and improve the performance of a process involving balanced exothermic reactions. The dimethyl ether (DME) direct synthesis from CO₂ and H₂ is considered as a case study. Different exploratory ways for the DME direct synthesis process development have been investigated based on modeling and simulation. Reactor- Heat exchanger, multifunctional reactor (reactor-heat exchanger-membrane separator), hybrid elementary block processes and a process involving the cooled reactor in a conventional process environment in the presence of additional unit operations and recycle loop are studied from different angles. Different optimization cases and strategies have been addressed which differ by the decision variables and the solving method. The different methodologies applied have demonstrated the relevance of the solutions obtained and the opening towards process innovation.At the equipment level, the profiles optimization represents the heart of the methodology. The results demonstrate the potential of multifunctional reactors: a CO₂ conversion per pass of 98%, a DME yield of 95% and the possibility to remove a distillation column are obtained. In order to assess the maximum achievable performance in a multifunctional reactor, a hybrid process of elementary blocks has been optimized. At the process scale, the reactor behavior has been studied to further understand the impact of the reactor integration in a recycle loop and to estimate the local and global effects on the multiple performance criteria. Based on various criteria (overall DME yield, overall CO₂ conversion, TRL, etc.), the comparison of the different designs revealed that a reduction of the equipment number by a factor of 11 is possible in the case of a multi-functional reactor choice

Afin de développer une chimie plus respectueuse de l'environnement, l'accès à de nouveaux procédés est nécessaire. Plus spécifiquement, dans le domaine de l'oxydation, l'utilisation d'oxydants toxiques doit être bannie, l'utilisation de solvants limitée et l'utilisation de catalyseurs recyclables développée. Dans ce contexte, deux approches " vertes " ont été explorées. La première d'entre elle consiste à éliminer ou remplacer l'acide acétique, additif qui, en présence de H2O2 et de complexes de Mn ou de Fe, favorise la formation exclusive d'époxydes lors d'oxydation d'alcènes. Pour cela, deux stratégies ont été testées. La première consiste à introduire dans la seconde sphère de coordination de complexes de Fe(III) et de Mn(II) des fonctions fluoroalcools devant faciliter l'activation d'H2O2. Comparés aux complexes analogues non modifiés, aucune amélioration de l'activité catalytique pour l'oxydation de cyclooctène n'est observée. Cependant, des complexes de Ni(II) et de Co(II) à ligands non modifiés ont démontré une activité catalytique élevée pour la photoproduction d'hydrogène. La seconde stratégie est basée sur le remplacement de l'acide acétique. Pour cela, en utilisant des billes de silice fonctionnalisées par des fonctions COOH (SiO2@COOH) comme co-réactif, une sélectivité significative en faveur de l'époxyde est observée lors de l'oxydation d'alcènes en présence de complexes de Mn(II) et de Fe(III) à ligand BPMEN. La seconde approche concerne des réactions d'(ép)oxydation sans solvant et utilisant des catalyseurs recyclables à base de polyoxométallates (POMs). Les catalyseurs SiO2@PMo et SiO2@PW, respectivement obtenus par greffage ionique de H3PMo12O40 ou H3PW12O40 sur des billes de silices fonctionnalisées par des fonctions pendantes NH2 (SiO2@NH2). Avec une faible charge catalytique, les deux catalyseurs sont efficaces lors de réactions d'oxydation avec une meilleure sélectivité que les POM libres. De plus, les deux catalyseurs réutilisés ont donné des conversions et des sélectivités similaires après deux recyclages
In order to develop a chemistry more respectful of the environment, access to sustainable processes is mandatory. More specifically, in the field of oxidation chemistry, use of toxic oxidants has to be banished, use of solvents limited and reusable catalysts developed. In this context, two types of greener approaches have been explored. The first approach concerns removal or replacement of acetic acid, an additive - in association with H2O2, favoring exclusive formation of epoxides with Mn and Fe metal complexes as catalysts. For this objective, two strategies have been explored. The first one consists in introducing fluoroalcohol functions in the second coordination sphere of metal complexes with pyridinophane-based ligand to easily activate H2O2. Those complexes did not enhance the catalytic activity for cyclooctene oxidation reactions in comparison to analogous Mn(II) and Fe(III) complexes with unmodified ligands. However, Ni(II) and Co(II) metal complexes with unmodified ligands display interesting catalytic activity for H2 photoproduction. The second strategy aimed to replace acetic acid. Using silica beads functionalized with COOH pendant arms (SiO2@COOH) as additive and H2O2 as oxidant, catalytic epoxidation reactions catalyzed by Mn(II) and Fe(III) metal complexes with BPMEN ligand displayed significant selectivity towards epoxide. The second approach concerns organic-solvent free (ep)oxidation processes with catalysts based on polyoxometalates (POMs). Catalysts SiO2@PMo and SiO2@PW, respectively obtained by ionic grafting of H3PMo12O40 or H3PW12O40 on silica beads functionalized with NH2 pending functions (SiO2@NH2), have been fully characterized. With low catalyst loading, both catalysts displayed efficient oxidation activity and better selectivity than the free POMs. Moreover, recovered beads gave similar conversion and selectivity after two recycling processes

Questo elaborato si basa su uno studio effettuato in collaborazione con l’istituto di ricerca ENI-Donegani durante il quale si è esaminata la possibilità di trattare attraverso un processo biologico accoppiato, anaerobico-aerobico, le acque derivanti dal trattamento idrotermale (HTL, hydrothermal liquefaction) della frazione organica del rifiuto solido urbano (FORSU). Lo studio si è incentrato sulla resa del processo in termini di biogas prodotto e sull’ identificazione dei composti presenti all’interno del refluo da trattare. Per il monitoraggio del processo biologico sono state condotte le seguenti analisi: GC-TCD (gas cromatografia-detector a conduttività termica) per l’identificazione della composizione del biogas; estrazione e analisi in GC-MS (gas cromatografo-spettrometro di massa) per l’identificazione degli acidi grassi volatili prodotti nel processo di digestione anaerobica; analisi del pH, dell’ammoniaca e del COD (Chemical Oxygen Demand) delle sostanze organiche disciolte. Per la caratterizzazione chimica dei composti organici idrosolubili non volatili stata effettuata una derivatizzazione, tramite sililazione, dei flussi di entrata e di uscita al reattore, con successiva analisi in GC-MS. L’analisi quantitativa è stata effettuata grazie al metodo dello standard interno. Dai risultati dello studio e stato riscontrato un problema di inibizione dei metanogeni e dei microrganismi aerobi con una maggiore produzione di VFAs rispetto a biometano. Tale inibizione è stata attribuita principalmente alla variabilità del sistema NH3/VFAs/pH ed alla presenza di molecole inibenti nel refluo acquoso (HTL-WW). Vista la maggiore produzione di VFAs potrebbe essere interessante valutare la separazione di questi composti ad alto valore economico utilizzati nelle industrie chimiche per la produzione di vernici, gomma, materie plastiche, pesticidi, e conservanti alimenti.

LIMA, Célia Maria de Souza Melo. A Gestão do Trabalho no Sistema Único de Assistência Social: Avaliação em Processo do Mundo do Trabalho na Secretaria do Trabalho e Desenvolvimento Social no Ceará. 2013. 213f. – Dissertação (Mestrado) – Universidade Federal do Ceará, Programa de Pós-graduação em Avaliação de Políticas Públicas, Fortaleza (CE), 2013.
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The domain of this study is the analysis of Social Assistance Policy, which is conceived as a public policy, focusing on the management of work in SUAS, from a perspective of valorization of workers. This evaluative research has its empirical field of study in the Department of Labor and Social Development - STDS - that coordinates and executes the policy of Social Assistance in the state of Ceara. Thus, the object of investigation circumscribes the following dimensions about the workforce in SUAS within the STDS: way of access to public service; employment contract and remuneration; SUAS workers’ identity as a new category in the construction process; an interdisciplinary perspective on the provision of a social assistance practice to ensure social protection; continuing education as a condition for the performance of interdisciplinarity and identity formation of SUAS workers. NOB/RH - SUAS is the central reference to structure the management of work, proposing the valorization of the workers, opposing the precariousness of labor relations, as an expression of changes in the world of work in the current civilization of capital. The theoretical foundations of this study focus on the examination of the world of work and the settings of the state in capitalism, discussing their impacts in SUAS. Therefore, theorists from the critical thinking will be discussed, specially within the Marxism’s framework, giving special attention to those contemporaneous authors such as Giovanni Alves and Ricardo Antunes, contemplating formulation of state from the perspective of Nelson Coutinho and Claus Offe. In the specific field of Social Assistence Policy and its management model embodied in SUAS, analysts’ formulations are included: Raquel Raichelis, Aldaíza Sposati, Alba Carvalho, Irma Moroni Silveira and Jucimere Silveira. The importance of this study is the fact that the insertion and position SUAS workers is a current issue, which expresses itself in dilemmas in the execution of socially necessary work in the function of public management and the provision of good social assistance service to ensure social protection. The methodology circumscribes a review in process founded on a predominantly qualitative research, combined with quantitative input.
O domínio analítico deste trabalho é a Política de Assistência Social, concebida como política pública de estado, com foco na gestão do trabalho no SUAS, sob a ótica da valorização dos trabalhadores. Esta pesquisa avaliativa tem como campo empírico de estudo a Secretaria do Trabalho e Desenvolvimento Social – STDS que coordena e executa a política de Assistência Social no Estado do Ceará. Assim, o objeto de investigação circunscreve as seguintes dimensões sobre o mundo do trabalho no SUAS no âmbito da STDS: forma de acesso ao serviço público; vínculo trabalhista e remuneração; identidade dos trabalhadores do SUAS, enquanto uma nova categoria em processo de construção; perspectiva da interdisciplinariedade na constituição de uma prática socioassistencial para garantir a proteção social; educação permanente como condição do exercício da interdisciplinaridade e da formação da identidade dos trabalhadores do SUAS. A NOB/RH-SUAS é a referência central para a estruturação da gestão do trabalho, propondo a valorização dos trabalhadores, contrapondo-se à precarização das relações trabalhistas, como expressão das transformações do mundo do trabalho na civilização contemporânea do capital. As bases de sustentação teórica deste estudo incidem no exame do mundo do trabalho e das configurações do Estado no capitalismo, discutindo os seus impactos no SUAS. Para tanto, serão trabalhadas bases teóricas no âmbito do pensamento crítico, especificamente nos marcos do marxismo, retomando autores contemporâneos estudiosos das temáticas em pauta, com destaque para Giovanni Alves e Ricardo Antunes, contemplando formulações de Estado a partir da ótica de Nelson Coutinho e Claus Off. No campo específico da Política de Assistência Social e do seu modelo de gestão consubstanciado no SUAS são retomadas formulações de analistas: Raquel Raichelis, Aldaíza Sposati, Alba Carvalho, Irma Moroni Silveira e Jucimere Silveira. A importância desse estudo está no fato de que a inserção e situação dos trabalhadores do SUAS circunscrevem questão atual, que se expressa em dilemas no exercício do trabalho socialmente necessário nas funções de gestão pública e na oferta dos serviços socioassistenciais continuados e de qualidade para assegurar a proteção social. O desenho metodológico circunscreve uma avaliação em processo, fundada em uma pesquisa predominantemente qualitativa, articulada com aportes quantitativos.

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O domÃnio analÃtico deste trabalho à a PolÃtica de AssistÃncia Social, concebida como polÃtica pÃblica de estado, com foco na gestÃo do trabalho no SUAS, sob a Ãtica da valorizaÃÃo dos trabalhadores. Esta pesquisa avaliativa tem como campo empÃrico de estudo a Secretaria do Trabalho e Desenvolvimento Social â STDS que coordena e executa a polÃtica de AssistÃncia Social no Estado do CearÃ. Assim, o objeto de investigaÃÃo circunscreve as seguintes dimensÃes sobre o mundo do trabalho no SUAS no Ãmbito da STDS: forma de acesso ao serviÃo pÃblico; vÃnculo trabalhista e remuneraÃÃo; identidade dos trabalhadores do SUAS, enquanto uma nova categoria em processo de construÃÃo; perspectiva da interdisciplinariedade na constituiÃÃo de uma prÃtica socioassistencial para garantir a proteÃÃo social; educaÃÃo permanente como condiÃÃo do exercÃcio da interdisciplinaridade e da formaÃÃo da identidade dos trabalhadores do SUAS. A NOB/RH-SUAS à a referÃncia central para a estruturaÃÃo da gestÃo do trabalho, propondo a valorizaÃÃo dos trabalhadores, contrapondo-se à precarizaÃÃo das relaÃÃes trabalhistas, como expressÃo das transformaÃÃes do mundo do trabalho na civilizaÃÃo contemporÃnea do capital. As bases de sustentaÃÃo teÃrica deste estudo incidem no exame do mundo do trabalho e das configuraÃÃes do Estado no capitalismo, discutindo os seus impactos no SUAS. Para tanto, serÃo trabalhadas bases teÃricas no Ãmbito do pensamento crÃtico, especificamente nos marcos do marxismo, retomando autores contemporÃneos estudiosos das temÃticas em pauta, com destaque para Giovanni Alves e Ricardo Antunes, contemplando formulaÃÃes de Estado a partir da Ãtica de Nelson Coutinho e Claus Off. No campo especÃfico da PolÃtica de AssistÃncia Social e do seu modelo de gestÃo consubstanciado no SUAS sÃo retomadas formulaÃÃes de analistas: Raquel Raichelis, AldaÃza Sposati, Alba Carvalho, Irma Moroni Silveira e Jucimere Silveira. A importÃncia desse estudo està no fato de que a inserÃÃo e situaÃÃo dos trabalhadores do SUAS circunscrevem questÃo atual, que se expressa em dilemas no exercÃcio do trabalho socialmente necessÃrio nas funÃÃes de gestÃo pÃblica e na oferta dos serviÃos socioassistenciais continuados e de qualidade para assegurar a proteÃÃo social. O desenho metodolÃgico circunscreve uma avaliaÃÃo em processo, fundada em uma pesquisa predominantemente qualitativa, articulada com aportes quantitativos.
The domain of this study is the analysis of Social Assistance Policy, which is conceived as a public policy, focusing on the management of work in SUAS, from a perspective of valorization of workers. This evaluative research has its empirical field of study in the Department of Labor and Social Development - STDS - that coordinates and executes the policy of Social Assistance in the state of Ceara. Thus, the object of investigation circumscribes the following dimensions about the workforce in SUAS within the STDS: way of access to public service; employment contract and remuneration; SUAS workersâ identity as a new category in the construction process; an interdisciplinary perspective on the provision of a social assistance practice to ensure social protection; continuing education as a condition for the performance of interdisciplinarity and identity formation of SUAS workers. NOB/RH - SUAS is the central reference to structure the management of work, proposing the valorization of the workers, opposing the precariousness of labor relations, as an expression of changes in the world of work in the current civilization of capital. The theoretical foundations of this study focus on the examination of the world of work and the settings of the state in capitalism, discussing their impacts in SUAS. Therefore, theorists from the critical thinking will be discussed, specially within the Marxismâs framework, giving special attention to those contemporaneous authors such as Giovanni Alves and Ricardo Antunes, contemplating formulation of state from the perspective of Nelson Coutinho and Claus Offe. In the specific field of Social Assistence Policy and its management model embodied in SUAS, analystsâ formulations are included: Raquel Raichelis, AldaÃza Sposati, Alba Carvalho, Irma Moroni Silveira and Jucimere Silveira. The importance of this study is the fact that the insertion and position SUAS workers is a current issue, which expresses itself in dilemmas in the execution of socially necessary work in the function of public management and the provision of good social assistance service to ensure social protection. The methodology circumscribes a review in process founded on a predominantly qualitative research, combined with quantitative input.

To study the process of territorial formation in the state of Bahia, we catagorised Feira de Santa in scaled sections, aiming to unveil euphemism and practices that create the powers supported by political and economic institutions on this geographical scale. The study focuses on the Sertão/territory as the locus of implementation of the territorial capital, a space which is understood as a dialectical relationship in its multiple scaled dimensions. The difference between litoral and sertão (coastal & dry land) explained under the Marxist orientation, falls within the social and territorial division of labour, where the social and political are subjected to the scrutiny of the capital in its multiple determinations. The reality is contradictory in its making and remaking the geography of the sertão (dry land) and signifies the concreteness of this movement. The starting point-is that Feira de Santana-is the scale of analysis, a place that serves as the foundation for the pursuit of know ledge about the territorial formation of the sertão. The construction/creation of the Bahian sertão establishes a challenge to consider the economic and political importance of the geographical location of Feira de Santana, as Princess and Portal of the Sertão. The research process has made it possible to understand the profound changes in its urban space and the historical context helping to establish the city as Princess of Sertão. The investigation led to the territorial analysis treated as the sertanejo- litorâneo relationship, which is the formation of the Brazilian nation. In conclusion, it is the Sertão that creates a Brazilian nationality, therefore this is a space that is instructed to carry a nomenclature full of stereotypes and multiple meanings. Feira de Santana is included in this place considered by many scholars as a space of no precise location, undefined, the fragile borders. There is a primitive accumulation and store of value in the territory. This condition causes a transformation into ground territory, where the idea of emptiness throughout space-time, is an essential context to the process of creating value for the capital. The Sertão, in the sertanejo area, assumes different meanings in constituting the streams of the capital.
Estudar o processo de formação territorial no estado da Bahia, tendo Feira de Santana como recorte escalar, visa desvelar circunlóquios e práticas que materializam os poderes sustentados por instituições políticas e econômicas sobre esta escala geográfica. O estudo enfoca o sertão/território como lócus da implantação da territorialização do capital, espaço que é compreendido enquanto relação dialética em suas múltiplas dimensões escalares. A diferença litoral versus sertão explicada sob o viés marxista se inscreve na divisão social e territorial do trabalho, onde o social e o político estão submetidos ao crivo do capital em suas múltiplas determinações. Se o real é contraditório no seu fazer e (re)fazer-se, a geografia do sertão é concretude desse movimento. O ponto de partida - Feira de Santana - é a escala de análise, lugar que serve de alicerce para a busca do conhecimento sobre a formação territorial do sertão. A construção/criação do sertão baiano institui um desafio para se pensar a importância econômica e política da localização geográfica de Feira de Santana, enquanto Princesa do Sertão e Portal do Sertão. O processo de investigação tornou possível perceber as profundas transformações no seu espaço urbano. Cada contexto histórico contribuindo para firmar a cidade como Princesa do Sertão. A investigação conduziu a análise territorial tratada como relação sertanejo-litorânea que é a formação da nação brasileira. Conclui-se que é no sertão que se produz uma nacionalidade brasileira porquanto esse não é somente um espaço que se incumbiu de carregar uma nomenclatura repleta de estereótipos e múltiplos significados. Feira de Santana se inclui nesse lugar considerado por muitos estudiosos como espaço de localização imprecisa, indefinida, de fronteiras fragilizadas. Território de acumulação primitiva e reserva de valor. Essa condição a conduz a ser chão transformado em território, onde a ideia de vazio foi ao longo do espaço-tempo, conteúdo essencial para o processo de valorização do capital. Sertão, sertanejo que assume diferentes significados para constituir-se vereda do capital.

Esta dissertação tem como objetivo analisar o processo de formação da agenda na política remuneratória e de reajustes salariais da Educação do Município de São Paulo surgida em 2006. Tal política, caracterizada por reajustes dos pisos remuneratórios da categoria, seguidos de incorporações nos padrões de vencimentos parceladas nos anos subsequentes, surge no governo Serra-Kassab (2005-2008) e continua durante os governos Kassab (2009-2012) e Haddad (2013-2016), proporcionando ganhos salariais reais à categoria durante o período. Procuramos compreender as formas pelas quais o tema da valorização dos profissionais de educação ascende à agenda governamental em 2006. Para tanto, buscamos entender como os fluxos de problemas, soluções e político convergem, possibilitando a abertura de uma janela de oportunidade para que a política fosse considerada e implementada, de acordo com o Modelo de Múltiplos Fluxos, de John Kingdon. Utilizamos, ainda, o Modelo de Equilíbrio Pontuado, de Frank Baumgartner e Bryan Jones, para entendermos como a imagem do problema da valorização dos profissionais de educação se relacionou com seu contexto institucional. A partir da análise da legislação municipal, de jornais sindicais e de entrevistas com os principais atores do processo, alcançamos os seguintes resultados: os fluxos de problemas, soluções e político convergiram no governo Serra-Kassab, por meio da atuação dos empreendedores de políticas públicas e dos diversos atores que participaram do processo, possibilitando a ascensão da valorização dos profissionais de educação à agenda governamental, demandando, dessa forma, atenção especial por parte dos formuladores de políticas públicas da Administração Municipal, que, juntamente com os sindicatos, chegaram, após um longo processo de negociação, a um formato acerca da política de remuneração e de reajustes salariais
This dissertation aims to analyze the process of agenda-setting in the remuneration and salary readjustments policy of the Education of the Municipality of São Paulo which emerged in 2006. This policy, characterized by adjustments of the minimum wage of the category followed by divided incorporations in the base salaries in subsequent years, was introduced by the Serra-Kassab government (2005-2008) and kept by the Kassab (2009-2012) and Haddad (2013-2016) governments, providing real wage gains to the category during this period. We seek to understand the ways in which the theme of valuing education professionals ascended in the governmental agenda in 2006. In order to do so, we need to understand how the streams of problems, policies and politics converged, allowing the opening of a window for this policy to be considered and implemented, according to John Kingdon\'s Multiple Streams Model. Frank Baumgartner and Bryan Jones Punctuated Equilibrium Model was also used in order to understand how the image of the problem of valuing education professionals was related to the institutional context. From the analysis of municipal legislation, trade union newspapers, and interviews with the main actors of the process, the following results were reached: the streams of problems, policies, and politics converged in the Serra-Kassab government through the action of public-policy entrepreneurs and of various actors who took part in the process, enabling the rise of the valorization of education professionals in the governmental agenda, thus demanding special attention from public policy makers of the Municipal Administration, who, paired with trade unions, came up with, after a long negotiation process, a plan for the remuneration policy and salary readjustments

The guidelines of The 2030 Agenda for Sustainable Development were very clear. New strategies need to be found to ensure a sustainable future. In this way, marine resources emerge as natural and renewable feedstocks to integrate a blue biorefinery framework and a circular economy approach. Through biomass conversion an integrated production of biofuels and value-added compounds can be designed, allowing the recovery of multiple compounds with lower environmental impacts and a sustainable economic growth. Pigments are natural compounds used in high-end applications due to their colour and high biological interest that can be found in several marine resources. However, the conventional techniques to recover them require the use of complex and time-consuming methodologies that may lead to the degradation and/or loss of stability of the compounds, high energy consumption, and low yields of extraction. Alternative solvents such as aqueous solutions of surfactants and ionic liquids (ILs) appear as more sustainable options that can improve thermal and chemical stability of pigments, obtain higher extraction yields, while minimizing the environmental impacts of the process. In this work, two procedures were developed to recover different pigments using alternative solvents, to overcome the bottlenecks found in the conventional methodologies. In the first work, a solid-phase extraction technique was used to fragmentate chlorophylls from xanthophyll. Then, to elute chlorophylls from AmberLite™ HPR900 OH resin, aqueous solutions of ILs revealed to be efficient solvents to valorize simultaneously xanthophyll and chlorophylls while reusing the resin in several new cycles of purification. The second work focused on the extraction of bacterioruberin pigment from Haloferax mediterranei with aqueous solutions of surfactants, being the non-ionic class the one that showed higher extraction yields. Moreover, the purification of bacterioruberin was also addressed by inducing a simple precipitation with ethanol as anti-solvent to recover proteins as a second added-value compound. In both works easy to implement and environmentally friendly procedures using water-based solvents were successfully proposed, being the operational conditions optimized to reduce both economic and environmental impacts, and to reach higher yields.
As diretrizes da Agenda 2030 para o Desenvolvimento Sustentável foram muito claras. Novas estratégias precisam de ser encontradas para garantir um futuro sustentável. Desta forma, os recursos marinhos surgem como matérias-primas naturais e renováveis para integrar uma estrutura de biorefinaria marinha e uma abordagem de economia circular. Através da conversão de biomassa, uma produção integrada de biocombustíveis e compostos de valor acrescentado pode ser projetada, permitindo a recuperação de vários compostos com impactos ambientais mínimos e um crescimento económico sustentável. Pigmentos são compostos naturais utilizados em aplicações de elevado padrão devido à sua cor e ao seu alto interesse biológico, podendo ser encontrados em diversos recursos marinhos. No entanto, as técnicas convencionais para recuperá-los requerem o uso de metodologias complexas e demoradas que podem levar à degradação e/ou perda de estabilidade dos compostos, alto consumo de energia e baixos rendimentos de extração. Solventes alternativos, como soluções aquosas de líquidos iónicos e surfactantes, aparecem como opções mais sustentáveis que podem melhorar a estabilidade térmica e química dos pigmentos, obter rendimentos de extração mais altos, enquanto minimizam os impactos ambientais do processo. Neste trabalho, foram desenvolvidos dois procedimentos para recuperar diferentes pigmentos utilizando solventes alternativos, a fim de superar as dificuldades encontradas nos métodos convencionais. No primeiro trabalho, uma técnica de extração em fase sólida foi usada para fracionar clorofilas e xantofilas. A seguir, para eluir as clorofilas da resina AmberLite™ HPR900 OH, as soluções aquosas de líquidos iónicos revelaram-se solventes eficientes para valorizar simultaneamente xantofilas e clorofilas, e reaproveitar a resina em vários novos ciclos de purificação. O segundo trabalho teve como foco a extração do pigmento bacterioruberina com soluções aquosas de surfactantes a partir da Haloferax mediterranei, sendo a classe dos não iónicos a que apresentou maiores rendimentos de extração. Além disso, a purificação da bacterioruberina também foi abordada através de uma simples precipitação induzida com etanol como anti-solvente para recuperar proteínas como um segundo composto de elevado valor comercial. Em ambos os trabalhos foram desenvolvidos com sucesso procedimentos de fácil implementação e ambientalmente sustentáveis recorrendo ao uso de solventes aquosos, sendo as condições operacionais otimizadas para reduzir os impactos económicos e ambientais, e permitir alcançar rendimentos mais elevados.
Mestrado em Engenharia Química

碩士
國立成功大學
創意產業設計研究所
103
The question of how to account for cultural value appears to be ever more present since the rise of the creative industries. Over the past decade, the design of methodologies, measurements and new terms has become a pressing agenda that seeks to inform the decisions that are made for the cultural sector. Accordingly, some have readily refashioned traditional economic tools while cultural advocates have directed their efforts to highlight the insufficiency of such approaches. Whilst consensus on the subject might not come at ease, the work of cultural and art economists, David Thorsby and Arjo Klamer respectively, provides a new framework for the understanding of cultural production that steps aside from traditional economics, on the pursuit of alternative evaluation techniques that don’t compromise cultural values under economic logics. From this strain of work, new gaps have come about as is the case of the process of valorization (Carnwath ＆ Brown, 2014) , i.e., the understanding of the interplay of values within processes of cultural production and how it might provide a window into the realization of cultural values. Attending to this call for empirical research, the present study poses the role of the curator as a meaningful case given her hybrid nature between artist and manager, and seeks to describe the process of valorization that contemporary art curators undertake for curatorial projects.

Dissertação de Mestrado Integrado em Engenharia Química apresentada à Faculdade de Ciências e Tecnologia
Among all environmental problems faced nowadays, climate change is undoubtedly the most imminent. Biofuels such as biogas may have a major role in the replacement of fossil fuels. Biogas is the main product of anaerobic digestion (AD) and can be used for producing energy in an efficient and eco-friendly way. The main objective of this work is the study of the AD process to assess the potential valorization of agro-industrial wastes through experimental and theoretical biochemical methane potential (BMP) prediction. In a first phase, 40 scientific papers were analyzed and was possible to obtain the BMP for 149 substrates. Then, an exhaustive analysis of these data was carried out through simple linear and multivariate polynomial regressions. Moreover, experimental tests of BMP and AD batch tests were used to evaluate the methane production of three substrates, namely winery wastewater (WW), tomato waste (TW) and banana peel waste (BW). Substrate-inoculum (S/I) ratios were optimized for WW and then applied to other substrates. Through the explorative analysis of the literature data, it was possible to verify that the BMP is a very complex parameter, making its prediction very hard. In fact, the methods for predicting this parameter referred in several papers are unsatisfactory since large differences are found between the predicted and the experimental BMP values. With the multivariate polynomial regressions performed in this study, it was possible to develop two models that present great potential for BMP prediction. From experimental tests, it was possible to verify that TW is the substrate with the highest potential for AD, followed by BW and lastly, with a lower potential, WW. The batch AD of WW revealed that the optimal S/I ratio is 0.5, which is in accordance with the literature. By using this S/I ratio it was possible to obtain 358.6 NmL gVS-1 of biogas for WW, 453.4 NmL gVS-1 for TW and 574.1 NmL gVS-1 for BW.This study demonstrated that BMP plays a fundamental role in the evaluation of a substrate potential for AD. It was possible to conclude that this parameter may be assessed in a simpler and faster way by theoretical models when compared to the experimental laborious methodologies. It was also possible to show that the substrates explored in this study can be valorized through an AD process.
De entre todos os problemas ambientais enfrentados hoje em dia, as alterações climáticas são, sem dúvida, as mais preocupantes. Os biocombustíveis, como o biogás, começam a ter um papel importante na substituição dos combustíveis fósseis. Este gás é o principal produto da digestão anaeróbia (AD) e pode ser usado para produzir energia de forma eficiente e ecológica. Existem diversos tipos de substratos orgânicos biodegradáveis que podem ser utilizados como substrato para na AD. Portanto, é de grande importância avaliar a biodegradabilidade e o potencial bioquímico de metano (BMP) destes.Este trabalho tem como principal objetivo o estudo do processo de AD, a fim de avaliar a possibilidade de valorização de resíduos agroindustriais. Através da análise de 40 artigos científicos, foi possível obter o BMP para 149 substratos diferentes. Após esta coleta foi realizada uma análise exaustiva desses dados através de regressões lineares simples e regressões polinomiais multivariadas. Foram realizados testes experimentais de BMP e de AD para avaliar o potencial de produção de metano de três substratos, nomeadamente de um efluente vinícola (WW), resíduo de tomate (TW) e resíduo de cascas de banana (BW). A razão substrato-inoculo (S/I) foi otimizada através da digestão do substrato WW, sendo depois aplicada aos restantes.Através da análise exploratória dos dados da literatura, foi possível verificar se o BMP é um parâmetro bastante complexo, fazendo com que a sua previsão seja difícil. Daí, os métodos para prever esse parâmetro referidos na literatura serem insatisfatórios. Através das regressões polinomiais multivariadas realizadas neste estudo foi possível desenvolver dois modelos que apresentam grande potencial no que toca à previsão do BMP. A partir dos testes experimentais BMP, foi possível verificar que o TW é o substrato com o maior potencial de AD, seguido do BW e, por último, com menor potencial, o WW. A AD do WW revelou que a razão S/I ideal, dentro dos valores testados, é de 0.5. Através desta razão S/I, foi possível obter 358.6 NmL gVS-1 de biogás para WW, 453.4 NmL gVS-1 para TW e 574.1 NmL gVS-1 para o BW.Este estudo demonstrou que o BMP desempenha um papel fundamental na avaliação do potencial de um substrato para AD e que é possível prever este parâmetro de forma mais simples e rápida em comparação com o procedimento experimental. Foi possível também mostrar que os substratos explorados neste estudo podem ser valorizados através de um processo AD.

Phosphorus (P) is a vital nutrient for plant development and food production. It is a key fertilizer constituent and no feasible substitute has been found yet. P is mainly obtained from phosphate rock, which is a non-renewable resource. This raises the critical issue of ensuring a continuous supply of P-fertilizers to feed mankind in the future. Therefore, it is of utmost importance to promote the circularity of P by recycling and recovering P from waste streams. The municipal solid waste (MSW) digestate is the result of the anaerobic digestion of MSW. It contains P but also contaminants, so currently it is mostly sent to landfill. This raises the question of how feasible is the extraction of P from MSW digestate for the production of a high-quality fertilizer. The present research is focused on MSW digestate utilization as a secondary P resource. In this PhD thesis, the extraction of P from MSW digestate using the electrodialytic (ED) process combined with struvite formation is explored for the first time. The ED process allows the separation of anions (e.g. PO4 3-) and cations (e.g. metals like Cu2+) present in MSW digestate by selectively transporting them across ion-exchange membranes under the influence of an electric field. Considering this extraction principle, P extraction experiments were conducted at lab-scale attempting to reach three purposes: i) extraction of the P available in the MSW digestate, ii) optimization of the energy performance of the ED process and iii) improvement of ED process, allowing also to recover nitrogen (N) from MSW digestate. The ED-extracted P was used for the synthesis of secondary struvite (MgNH4PO4·6H2O), through chemical precipitation. Alternative sources of N and magnesium (Mg) needed for the synthesis of struvite were explored, named seawater (as Mg source) and N contained in the MSW digestate itself. Acting as a slow-release fertilizer, struvite releases nutrients to the soil along the time. The agronomic efficacy of the secondary struvite, obtained using the P extracted from MSW digestate was assessed, first in incubation trials (to study the evolution with time of P in the soil) and then in pot trials, where plant growth in struvite fertilized soils and in soils fertilized with a commercial fertilizer was compared. The research findings show that up to 90% of P present in MSW digestate could be extracted using ED and converted to struvite. Being a negatively charged specie, P moved from the MSW digestate and concentrated in the anolyte solution when a 50 mA electric current (1.0 mA cm-2) was applied. During ED process, the extraction of P was strongly dependent on the pH of MSW digestate, and a low pH (2.5-3.0) was needed to enhance the P solubilization from the MSW digestate. This was achieved by using the electrochemical reaction occurring at the anode (originates H+ ions), thus avoiding the addition of chemicals. The benefit of this electrochemical reaction was fundamental for the implementation of another strategy for P extraction: a dual-stage approach. In the first stage, the electrode (+) was placed in contact with the MSW digestate, causing a faster acidification of the digestate while P remains in this compartment. When the pH reached 3 in the MSW digestate suspension, the electrode (+) was moved into the anolyte compartment and the solubilized P migrated from the MSW digestate compartment to the anode compartment. This strategy effectively reduced the time required for the ED extraction of P (to 7 days) and consequently decreased the energy consumption (≈30%). The extraction of another important nutrient, N, from MSW digestate was also pursued by adding a gas permeable membrane (GPM) to the cathode of the ED cell, while the extraction of P was taking place. N moved from the MSW digestate into the cathode compartment as NH4 + (by electromigration), and there it was converted to gaseous NH3 and collected by the GPM into a clean N solution, leaving behind the heavy metals at the cathode solution. The clean N solution was subsequently used with success as a source of N in the synthesis of secondary struvite. The combination of these two membrane technologies - ED and GPM - for simultaneous extraction of P and N was explored in this work for the first time, and contributed to the sustainability of the synthesis of secondary struvite. The secondary struvite produced in this work using P recovered from MSW digestate proved to be of high quality, even when alternative materials were used instead of synthetic ones during its precipitation. Its action as an effective P biofertilizer is similar to that of a commercial synthetic fertilizer. The major outcome of this work is the proof of concept of an innovative process that combines ED and GPM for the recycling of P from MSW digestate. The contaminant-free biofertilizer, produced at lab scale, widens the possibilities for the large scale recycling of P and for the implementation of efficient strategies to close P-nutrient cycling, thus contributing to a more sustainable resource management.
O fósforo (P) é um nutriente vital para o desenvolvimento das plantas e a produção de alimento. É um dos principais constituintes dos fertilizantes e até ao momento ainda não foi encontrado nenhum outro elemento que o possa substituir. O P é obtido principalmente da rocha fosfatada, que é um recurso não renovável. Isto suscita uma questão fundamental sobre como garantir um fornecimento contínuo de P para a produção de fertilizantes fosfatados necessários para produzir alimento para a humanidade, no futuro. Portanto, é de extrema importância promover a circularidade do P por meio da sua reciclagem e da recuperação a partir de fluxos de resíduos. O digestato de resíduo urbano (RU) é o resultado do processo de digestão anaeróbia. Este contém P, mas também contaminantes, pelo que atualmente, o digestato de RU é na maioria das vezes encaminhado para aterro. Isto levanta a questão de saber quão viável é a extração do P do digestato de RU para a produção de um fertilizante de elevada qualidade. O presente trabalho de investigação é focado na utilização do digestato de RU como um recurso secundário de P. Nesta tese é explorada pela primeira vez a extração de P do digestato de RU utilizando o processo electrodialítico (ED) combinado com a precipitação de estruvite. O processo ED permite a separação de aniões (p. ex. PO4 3-) e catiões (p. ex., metais como Cu2+) presentes no digestato de RU, transportando-os seletivamente através de membranas de troca iónica, sob a influência de um campo elétrico. Considerando este princípio, as experiências de extração de P foram realizadas à escala laboratorial, tendo em conta três objetivos: i) a extração do P disponível no digestato de RU, ii) a otimização do desempenho energético do processo ED e iii) a melhoria do processo ED através da conjugação com a recuperação do azoto (N) do digestato de RU. O P extraído durante o processo ED foi utilizado para a síntese de estruvite secundária (MgNH4PO4·6H2O), através do processo de precipitação química. Para a síntese desta estruvite foram exploradas fontes alternativas de N e magnésio (Mg), nomeadamente a água do mar (como fonte de Mg) e o N contido no próprio digestato de RU. A estruvite é um fertilizante de libertação lenta, o que significa, que fornece nutrientes ao solo ao longo do tempo. A eficácia agronómica da estruvite secundária, obtida com o P extraído do digestato de RU, foi avaliada, primeiramente em ensaios de incubação (para estudar a evolução do P no solo, ao longo do tempo) e depois em ensaios em vaso, onde o crescimento da planta num solo fertilizado com estruvite e num solo fertilizado com um fertilizante comercial foi comparado. Os resultados mostram que cerca de 90% do P que está presente no digestato de RU pode efetivamente ser extraído através do processo ED e convertido em estruvite. Por ser uma espécie carregada negativamente, o P foi extraído do digestato do RU e foi concentrado no anólito, após ter sido aplicada uma corrente elétrica de 50 mA (1,0 mA cm-2). Durante o processo ED observou-se que a extração de P era fortemente dependente do pH do digestato de RU, e que era necessário um pH baixo (2,5-3,0) para aumentar a sua solubilização. Isto foi conseguido através da utilização da reação eletroquímica que ocorre no ânodo (origina iões H+ ), o que evitou a adição de produtos químicos. Os efeitos benéficos desta reação eletroquímica foram fundamentais para a implementação de uma outra estratégia para a extração de P: uma extração em duas fases. Na primeira etapa, o elétrodo (+) foi colocado em contato com o digestato de RU, o que causou uma acidificação mais rápida do digestato enquanto o P permaneceu neste compartimento. Quando o pH da suspensão de digestato de RU atingiu o valor de 3, o elétrodo (+) foi movido para o compartimento do anólito e o P que tinha sido solubilizado durante a primeira etapa migrou do compartimento de digestato de RU para o compartimento do anólito. Esta estratégia permitiu uma redução efetiva do tempo necessário para a extração de P pelo processo ED (para 7 dias) e, consequentemente, uma diminuição do consumo de energia (≈30%). A extração de outro nutriente importante, o N, do digestato de RU também foi realizada, ao mesmo tempo que ocorria a extração de P, adicionando uma membrana permeável a gases (GPM) ao cátodo da célula electrodialítica. O N era extraído do digestato de RU para o compartimento do cátodo, na forma de ião NH4 + (por electromigração), e lá era convertido em NH3 gasoso e capturado pela GPM produzindo uma solução limpa rica em N, deixando para trás os metais pesados na solução do cátodo. A solução limpa rica em N foi subsequentemente usada com sucesso como fonte de N na síntese de estruvite secundária. A combinação destas duas tecnologias de membrana - ED e GPM - para extração simultânea de P e N foi explorada neste trabalho pela primeira vez, e contribuiu para a sustentabilidade da síntese de estruvite secundária. Neste trabalho, a estruvite secundária produzida utilizando o P recuperado do digestato de RU apresentou uma elevada qualidade, mesmo quando durante a sua precipitação foram utilizados materiais alternativos em vez de materiais sintéticos. A sua ação como um biofertilizante fosfatado foi semelhante à de um fertilizante sintético comercial. O principal resultado desta tese é a prova de conceito de um processo inovador que combina a técnica electrodialítica com uma membrana permeável a gases para a reciclagem de P a partir do digestato de RU. O biofertilizante livre de contaminantes, produzido à escala de laboratório, amplia as possibilidades para a reciclagem do P em larga escala e para a implementação de estratégias eficientes para fechar o ciclo do nutriente P, contribuindo assim para uma gestão mais sustentável dos recursos.
Programa Doutoral em Ciências e Engenharia do Ambiente

Infants have a low developed immune system, which raises the possibility of microbial infections when exposed to contaminated foods. Infant foods, especially powdered infant formula (PIF), have been epidemiologically linked with various food-borne infections. Staphylococcus aureus is one of the major pathogens that could be related to these infant food outbreaks. Though traditional thermal processing and the use of synthetic antibiotics effectively kill food-borne pathogens, they have been found to degrade quality attributes that are objectionable to consumers. To resolve this issue, notable efforts have been taken, among which the use of natural antimicrobials is the foremost approach. Pomegranate peels are known to exhibit various groups of phytochemical compounds consisting of polyphenols, anthocyanins, flavonoids, phenolic acids, and hydrolysable tannins at significant levels compared to fruit arils. The hydrolysable tannins present within pomegranate peel have been known for their noteworthy antimicrobial properties. However, owing to the lack of proper value addition methods, the antimicrobial property of pomegranate peels is not still utilized to their full potential. This urges the need to develop a process technology that could utilize pomegranate peels as a robust natural antimicrobial compound. In the present work, a process protocol is being developed that aids to determine the antimicrobial activity of encapsulated pomegranate peel extract against strains of S. aureus isolated from PIF. Unit operations namely drying, grinding, extraction and encapsulation are vital for the appropriate use and value-addition of the pomegranate peels as a natural antimicrobial. For the maximum recovery of phytochemical compounds, the fresh pomegranate peels were dried using the microwave vacuum drying method. The drying experimental runs were performed on varied ranges of microwave power (175, 330, 485 W) and vacuum pressure (10, 15, 20 kPa) using a face‐centered composite design. Optimized condition for microwave- vacuum drying of pomegranate peel (within the chosen range) was observed as 276 W microwave power and 10 kPa vacuum. At the optimized condition, the phytochemical compounds targeted were considerably preserved. Amino acid analysis of dried peels at optimized conditions exhibited the retention of 11 amino acids at significant levels with glycine possessing the highest concentration 5.93 mg/g. The dried pomegranate peel was ground using conventional and cryogenic grinding techniques. From the numerous powder properties studied, say bulk density, true density, porosity, product temperature, moisture content, water activity, phytochemical compounds, and surface morphology analysis, it was concluded that the properties of the cryogenically ground peel powders were superior to that of the conventionally produced peel powders. The extract from cryogenically ground pomegranate peel powder, containing maximum phytochemical compounds (with the highest recovery of hydrolysable tannins) was extracted using pulsed system ultrasound. The process variables in total hydrolysable tannin extraction were modeled and optimized by an artificial neural network and genetic algorithm respectively. The optimal extraction conditions attained for process variables were; solvent concentration of 56%, solvent-feed ratio of 26.5 mL/g, extraction time of 15 min, and ultrasound amplitude of 50% respectively. Pulsed system ultra-sonication significantly augmented total hydrolysable tannins of pomegranate peel extract to 98.12 mg TAE/g compared to 50.14 mg TAE/g with conventional extraction. The Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC) analyses established that pomegranate peel extract produced at above optimal conditions contained a significant amount of hydrolysable tannin compounds (gallic acid and tannic acid derivative) than conventional extraction methods. The pomegranate peel extract was encapsulated using external gelation technique. The process variables in encapsulation were modeled and optimized by Box-Behnken design. The encapsulation efficiency and properties of encapsulate were found to be optimum at 4% sodium alginate concentration, 2.5% CaCl2 concentration, and 30% PPE concentration. The encapsulation efficiency at the optimized condition was 83.65%. A comparative study was performed to evaluate the properties of encapsulates produced by external gelation (at its optimum conditions) and spray drying. The encapsulates were analyzed for various physical properties, phytochemical parameters, release profile, storage stability, and thermal stability. The performed analyses revealed the superiority of the encapsulates produced by external gelation over spray drying. Further the thermal stability and antibacterial activity of developed pomegranate peel extract encapsulates was carried out. The outcomes revealed that the zone of inhibition (ZOI) and minimum inhibitory concentration (MIC) of encapsulated pomegranate peel extract against S. aureus (ATCC 25923) identified in PIF were 32 ± 0.01 mm, and 300 μg/mL respectively. The outcomes are promising and recommend the possibility of utilizing encapsulated pomegranate peel extract as natural antimicrobials or as a systemic natural antibiotic replacing the synthetic antibiotics for inactivation of S. aureus strains isolated from powdered infant formula at an industrial level.

Mestrado de dupla diplomação com a UTFPR - Universidade Tecnológica Federal do Paraná
During wine production a large amount of waste (grape pomace) is generated. This material is considered a rich source of bioactive compounds, thus being of interest for cosmetics, pharmaceutical and food industries. However, it is susceptible to microbial degradation due to its high moisture content, and therefore drying is frequently considered an essential process for grape pomace conservation and stabilization. Nevertheless, drying conditions such as temperature and time may affect grape pomace bioactive potential. Because drying represents a high energy consumption, an alternative for reducing the energy costs is the use of intermittent operation, which operates with transient inputs of air conditions, such as the supply temperature. Intermittent drying, in addition to promoting lower energy consumption, also enables less damage to heat-sensitive materials. In the present work, modeling of the drying process of grape skins and seeds from red wine grape pomace was performed at temperatures of 40 °C, 55 °C and 70 °C, both for drying in the conventional and in the intermittent mode, with intermittences of 5 and 10 minutes. Moreover, total phenolics content (TPC), total flavonoids content (TFC) and antioxidant activity (DPPH and reducing power assays) were determined by spectrophotometric methods before and after the drying process at the proposed conditions. The identification and quantification of phenolic compounds (non-anthocyanins and anthocyanins) was carried out through LC-DAD-ESI-MS/MS analysis. Modeling results showed that, among the 8 models tested for the conventional drying, the one that best suited the experimental data, for both skin and seeds, was the Approximation of diffusion model and therefore can be used in following studies to optimize drying parameters. For the intermittent drying, experimental data could be predicted by the intermittent drying model with a global maximum deviation of 10%. Results of TPC, TFC and antioxidant activity assays showed that conventional drying had the highest impact on lowering the content of bioactive compounds both on grape skins and seeds. By the contrary, the present work showed that intermittent drying can provide grape pomace samples with higher content of bioactive compounds and higher antioxidant activity, with 10 minutes intermittence in general performing best when compared to 5 minutes intermittent period, particularly for grape seeds pomace samples.
Durante a produção do vinho, uma grande quantidade de resíduos (bagaço de uva) é gerada. Este material é considerado uma rica fonte de compostos bioativos, sendo de interesse para diversas indústrias. No entanto, o mesmo é suscetível à degradação microbiana devido ao seu alto teor de humidade e, portanto, a secagem é frequentemente considerada um processo essencial para a sua conservação e estabilização. No entanto, as condições de secagem, podem afetar o potencial bioativo do material. Como a secagem representa um alto consumo de energia, uma alternativa para redução dos custos é a utilização de operação intermitente, que, além de promover menor consumo de energia, possibilita menos danos aos materiais termossensíveis. No presente trabalho a modelação do processo de secagem de cascas e sementes de uva de vinho tinto foi realizada para temperaturas de 40°C, 55°C e 70°C, tanto para secagem no modo convencional quanto no modo intermitente, com intermitências de 5 e 10 minutos. Além disso, o teor de compostos fenólicos totais, o teor de flavonóides totais e a atividade antioxidante (ensaios de DPPH e poder redutor) foram determinados por métodos espectrofotométricos antes e após o processo de secagem. A identificação e quantificação dos compostos fenólicos (não-antocianinas e antocianinas) foram realizadas por LC-DAD-ESI-MS/MS. Os resultados da modelação mostraram que, para a secagem convencional, o que mais se adequou aos dados experimentais, tanto para a casca quanto para sementes, foi o modelo de Aproximação de difusão e, portanto, pode ser utilizado em estudos posteriores para otimizar os parâmetros do processo. Para a secagem intermitente, os dados experimentais puderam ser previstos pelo modelo de secagem intermitente com um desvio máximo global de 10%. Os resultados dos ensaios de compostos fenólicos, flavonoides e atividade antioxidante mostraram que a secagem convencional teve o maior impacto na redução do conteúdo de compostos bioativos tanto na casca como na semente da uva. O presente trabalho mostrou que a secagem intermitente pode fornecer amostras de bagaço de uva com maior teor de compostos bioativos e maior atividade antioxidante, com a intermitência de 10 minutos demonstrando em geral melhor desempenho quando comparada ao período intermitente de 5 minutos, principalmente para amostras de sementes de uva.

Im Rahmen der vorliegenden Arbeit wurden die ausgekoppelten Rückstände einer stoffgeführten Veredelungskette zur stofflichen Nutzung von Braunkohle charakterisiert, welche aus den Wandlungsstufen Extraktion mit Toluol, Niedertemperaturkonversion (katalytische Pyrolyse und Reaktivextraktion mit superkritischen Lösungsmitteln) und Vergasung besteht. Schwerpunktmäßig wurde die Vergasungsreaktivität der Rückstände untersucht, da sie in der letzten Prozessstufe der Vergasung zugeführt werden. Die Variabilität der Reaktivität der Ausgangsstoffe diente hierzu als Maßstab zur Bewertung der Vergasungsreaktivität der Rückstände der Prozesskette. Im Rahmen der Charakterisierung wurden charakteristische Stoffeigenschaften identifiziert, welche die Vergasungsreaktivität der betrachteten Rohstoffe primär beeinflussen. Dazu zählen die Aromatizität und die Aschezusammensetzung. Auf dieser Basis wurden die Rückstände der Prozesskette bewertet und interpretiert. Es wurden verschiedene experimentelle Methoden (zwei Thermowaagen und ein Festbettverssuchstand) verwendet und gegenseitig validiert. Daneben wurde geprüft, ob die Reaktivität einer Mischung, bestehend aus den Rückständen der Prozesskette, aus den Reaktivitäten der Einzelkomponenten vorausberechnet werden kann und drei Grenzfälle abgeleitet. Basierend auf den im Rahmen der Arbeit generierten konsistenten Datensätzen wurde ein halbempirisches Modell zur Vorausberechnung der Vergasungsreaktivität von Braunkohlen und deren Veredelungsprodukten hergeleitet. Das Modell berücksichtigt die Zusammensetzung der organischen Substanz sowie die Zusammensetzung der anorganischen Substanz einer Kohleprobe und wurde unter Einbezug weiterer Kohleproben erfolgreich validiert.

Dissertação de Mestrado Integrado em Engenharia Química apresentada à Faculdade de Ciências e Tecnologia
O aumento das preocupações relativas à quantidade e qualidade de água de consumo, levou à necessidade de regulamentar a descarga de efluentes para o meio ambiente. De salientar as águas-ruças que dada a sua elevada carga orgânica, a sua baixa biodegradabilidade e o seu carácter fitotóxico, necessitam de um processo de tratamento eficiente. Contudo esses efluentes possuem na sua constituição elevadas quantidades de compostos fenólicos que devidamente isolados e nas concentrações adequadas, apresentam propriedades antioxidantes e anti-inflamatórias, benéficas na saúde humana. Este trabalho teve como principal objetivo integrar um processo de valorização e tratamento destes efluentes recorrendo a processos de separação por membranas, processo de adsorção/permuta iónica e processos de oxidação avançados.Dois lotes do mesmo efluente obtidos pelo método de extração tradicional, foram submetidos a um pré-tratamento que visou a redução do diâmetro de partículas para a etapa de ultrafiltração (UF). Nesta etapa do estudo considerou-se o efluente tratado pelo crivo de 75 µm com valores de rejeição de TPh de ~1%, 6 – 8% de CQO e 31 – 35% de SST para os diferentes lotes. O pré-tratado foi sujeito a um processo de UF, tendo como objetivo a separação de compostos de elevado peso molecular. O efeito das variáveis pressão transmembranar (PTM) e temperatura na remoção de CQO e TPh foi estudado usando duas membranas de UF. Obtiveram-se como condições ótimas de operação, 1.5 bar, 25 °C e a escolha da membrana de maior MWCO. De seguida, procedeu-se ao ensaio de concentração para as condições selecionadas, obtendo-se uma remoção de CQO e TPh de 20,6% e 26,8%, respetivamente.Partindo do permeado obtido no processo de UF e tendo como objetivo a obtenção de um permeado depurado e um concentrado rico em compostos fenólicos, realizou-se o estudo da filtração com uma membrana de nanofiltração (NF). No âmbito deste estudo, avaliou-se a influência das variáveis queda de pressão (¿P), temperatura e pH, na remoção da CQO, TPh e no fluxo de permeado tendo por base um planeamento fatorial a dois níveis e do qual se obteve as seguintes condições ótimas: 18 bar, 25 °C e pH de 2.7, correspondentes a uma remoção de CQO e TPh de 82,9% e 93,8%, respetivamente.O concentrado da NF, foi depois submetido a um processo de adsorção com objetivo de isolar a fração fenólica. Para isto, recorreu-se a dois tipos de adsorvente, um não iónico e outro aniónico de base forte. O efeito do pH foi estudado, tendo-se obtido para ambas as resinas um pH ótimo de 7. A resina não iónica e aniónica, apresentaram respetivamente, uma eficiência de adsorção máxima de TPh de 57,2% e 73,2% para uma concentração de 120 g resina / L. Os ajustes das isotérmicas obtidas foram conseguidos com o modelo de Freundlich.Por forma a cumprir a legislação relativos aos limites de descarga, submeteu-se o permeado da NF a um tratamento final pelo processo de Fenton. O efeito das razões [H2O2] / CQO (w/w) e [H2O2] / [Fe2+] (M/M) na remoção de CQO e TPh foram estudados, através de um planeamento fatorial a dois níveis, tendo-se obtido um ótimo de 2.1 para a razão [H2O2] / CQO e 12.0 para a razão [H2O2] / [Fe2+], sendo estes correspondentes a uma remoção de 53,1% de CQO e 100% de TPh.Os resultados obtidos demonstram que existe potencial para a obtenção de compostos fenólicos a partir dos resíduos de azeite, sendo para isso necessário a integração de um conjunto de processos de separação.
The increasing awareness regarding quality of drinking water is leading to the need of regulating effluents discharge. Of especial concern are olive-mill wastewater due to their high organic load content, low biodegradability and phytotoxic content. Thus, efficient treatment is required. However, those effluents have high content of phenolic compounds which, when isolated and in suitable concentrations, show antioxidant and anti-inflammatory proprieties important to human health. The aim of the research carried out consisted in the valorization of olive-mill wastewater by membrane separation processes, adsorption/ionic exchange processes and advanced oxidation processes (Fenton).Two lots from the same effluent were obtained by the traditional extraction underwent a pre-treatment aiming to reduce the diameter of particles before UF. The optimal sieve was 75 µm with TPh rejection values of ~1%, 6 – 8% of COD and 31-35% of TSS for the two different lots.The sieved effluent was used for UF in order to separate compounds with high molecular weight. The effect of transmembrane pressure (TMP) and temperature on the removal of COD and TPh in two UF membranes was studied. The optimal operating conditions were 1.5 bar and 25 °C. Moreover, the larger MWCO membrane. Should be used, it with these conditions concentration was performed, obtaining a COD and TPh removal of 20,6% and 26,8%, respectively.In order to obtain a purified permeate and a phenolic-rich concentrate, the permeate obtained from the UF process was treated by nanofiltration (NF). The influence of ¿P, temperature and pH in the removal of COD, TPh and permeate flow were studied using a 2-level full factorial experimental design. The following optimal conditions were obtained: 18 bar, 25 °C and a pH 2.7, which corresponded to 82,9% and 93,8% of COD and TPh removal, respectively for the concentration process.With the objective of isolating the phenolic fraction present in the NF concentrate was subjected to an adsorption process. For that purpose, two types of adsorbents were used, a non-ionic and an anionic of strong base. The effect of pH was studied and for both resins an optimal pH of 7 was achieved. A maximum TPh adsorption of 57,2% and 73,2% for the non-ionic and anionic resins, respectively, were achieved for a S/L ratio of 120. Experimental equilibrium data were well fitted with the Freundlich model.To fulfill the discharge limits in order to comply with the legislation, the permeate obtained by NF was treated by Fenton’s process. The effect of [H2O2]/COD (w/w) and [H2O2]/[Fe2+] (M/M) in COD and TPh removal were studied using 2-level full factorial experimental design, where 2.1 was the optimum for [H2O2]/CQO ratio and 12.0 for [H2O2]/[Fe2+] ratio, corresponding to 53,1% of COD and 100% of TPh removal.OMW showed to be an interesting source of phenolic compounds, thus being necessary to integrate a set of separation processes.