Le but de notre projet était de mettre au point un procédé éco-compatible d’organocatalyse asymétrique hétérogène en flux continu. Pour réaliser ce procédé, nous avons choisi d’utiliser la cupréine, un alcaloïde dérivé de la quinine comme organocatalyseur bifonctionnel. La silice (un matériau inorganique mésoporeux) a été choisie comme support pour l’hétérogénéisation du catalyseur. La cupréine immobilisée sur silice a ensuite été testée comme organocatalyseur de la réaction d’addition de Michael asymétrique entre le trans-β-nitrostyrène (accepteur de Michael) et le diméthyl malonate (donneur de Michael) en condition de flux continu.Nous avons tout d’abord immobilisé la cupréine sur deux types de silice selon trois stratégies différentes. Chaque stratégie nous a permis d’obtenir le support greffé avec des quantités de cupréine allant de 0,2 à 0,4 mmol par gramme de silice, ainsi que des silices greffées possédant des caractéristiques différentes selon les stratégies envisagées.L’évaluation de l’activité catalytique de la cupréine greffée sur silice a ensuite été réalisée en milieu hétérogène en batch. Différents solvants biosourcés ont alors été testés comme solvants alternatifs pour la réaction d’addition de Michael. Le 2-MeTHF s’est révélé être un bon solvant et a été choisi pour les expériences de catalyse en flux continu. Les résultats obtenus en catalyse avec la cupréine greffée sur silice sont comparables à ceux en milieu homogène (excès énantiomériques supérieur ou égale à 85 % et conversion supérieure à 96 %) exceptés pour la fréquence de rotation (TOF, mol de substrat converti/mol de catalyseur/durée de réaction) qui est trois fois plus faible en milieu hétérogène (0,2 h-1 pour 0,6 h-1 en milieu homogène).Enfin, cette réaction d’addition de Michael a été réalisée en flux continu avec les différentes silices greffées. La fréquence de rotation de la cupréine a été multipliée par deux (0,4 h-1) et le nombre de rotation (TON, mol de substrat converti/mol de catalyseur) a lui aussi été augmenté, passant de 16 en milieu hétérogène en batch à 63 en condition de flux continu. Finalement, différents dérivés du trans-β-nitrostyrène (Chloré, phénolique et méthoxy en position 4) ont été testés avec succès.Ainsi, à notre connaissance, nous avons réalisé la première réaction d’addition de Michael entre le trans-β-nitrostyrène et le diméthyl malonate, organocatalysée en milieu hétérogène en batch et en flux continu par la cupréine immobilisée sur silice, en utilisant un solvant biosourcé. Nous avons réussi à mettre au point le procédé de catalyse hétérogène en flux continu permettant de recycler facilement le catalyseur et aussi d’augmenter la productivité de la cupréine immobilisée par rapport au milieu hétérogène en batch, tout en conservant une conversion et une énantiosélectivité équivalente à celles en milieu homogène. / The aim of our project was to develop an eco-friendly process based on heterogeneous asymmetric organocataysis in continuous flow conditions. To succeed in this development, we chose to use a quinine-derived bifunctional organocatalyst: cupreine. Silica, a mesoporous inorganic material, was chosen as the support to immobilize this organocatalyst. The grafted cupreine was then tested as catalyst for the asymmetric Michael addition between the trans-β-nitrostyrene (Michael acceptor) and the dimethyl malonate (Michael donor) in continuous flow condition.First, we immobilized the catalyst on two types of silica, following three different strategies. The various cupreine-grafted silicas we obtained were functionnalized with 0.2 to 0.4 mmol of cuprein per gram of silica. Each one of them possessed specific characteristics depending of the followed strategy.The assessment of the catalytic activity of immobilized silica was then performed in batch condition. Different bio-based solvents were used for the Michael addition. 2-MeTHF was chosen as the best solvent among those tested and used in continuous flow. Immobilized cupreine proved to be as efficient in heterogenous condition as in homogenous (enantiomeric excess was superior or equal to 85 % and conversion better than 96 %), except for turn over frequency (TOF, mol of converted substrate/mol of catalyst/reaction time) which is three times lower in hetereogeneous condition (0.2h-1 to 0.6 h-1 in homogenous condition).Michael addition of trans-β-nitrostyrene to dimethyl malonate was then realized in continuous flow condition, using the various silica-supported catalysts. Turn over frequency of cupreine was doubled (0.4 h-1) and the turn over number (mol of converted substrate/mol of catalyst) increased from 16 to 63 in continuous flow condition. Derivatives of trans-β-nitrostyrene (chlorinated, phenolic and methoxylated in position 4) were successfully tested in continuous flow.To the best of our knowledge, we realized the first asymmetric Michael addition between trans-β-nitrostyrene and the dimethyl malonate, catalysed by silica-supported cupreine in batch and in continuous flow, using a bio-based solvent.We successfully developed an eco-friendly process based on heterogeneous organocatalysis in continuous flow. This process favorited an efficient recycling of the supported catalyst, and increased the productivity of grafted cupreine compare to the heterogeneous condition in batch. The enantioselectivity of the cupreine for this reaction was similar in both homogeneous and heterogeneous conditions.

Ce manuscrit décrit les travaux de doctorat réalisés au sein du laboratoire du Pr. Charette entre 2015 et 2019. Ceux-ci s’inscrivent dans deux thématiques de recherche différentes : le développement de nouvelles stratégies d’amidation et le développement de nouvelles méthodologies de cyclopropanation. La synthèse de liaisons amides est, encore aujourd’hui, un défi pour la communauté chimique. En effet, le développement de méthodologies simples, robustes, économes en atomes, et plus respectueuses de l’environnement reste l’une des priorités de recherche en chimie organique. Afin d’apporter une contribution à ce domaine, une méthodologie de synthèse d’amides a été développée en utilisant le diphénylsilane en tant qu’agent de couplage. Celui-ci est disponible commercialement, stable et peu onéreux. De plus, il ne génère qu’un siloxane et du dihydrogène gazeux en fin de réaction. La méthodologie mise au point a également pu être appliquée à la synthèse d’une série de di- et tripeptides. L’utilisation du motif cyclopropanique n’a cessé de prendre de l’ampleur dans le secteur pharmaceutique. En effet, celui-ci peut influer sur différents paramètres cruciaux dans le développement de molécules biologiquement actives. Le développement de nouvelles méthodologies de cyclopropanation est donc un domaine pertinent. La synthèse de borocyclopropanes est particulièrement intéressante : en effet, ces composés peuvent permettre de créer de la diversité structurale via une fonctionnalisation du boronate. Afin d’obtenir un procédé de synthèse de ces composés simple, robuste et plus « vert », une approche photochimique utilisant la technologie en débit continu a été favorisée. Une réaction de borocyclopropanation photorédox de styrènes a pu être mise au point ; celle-ci est réalisée sous irradiation UV-A en présence de xanthone en tant que photocatalyseur. Les études menées afin d’élucider le mécanisme ont permis de conclure que cette transformation se déroulait selon deux cycles catalytiques photorédox concomitants. Finalement, un nouveau réactif diiodé comportant une fonction ester boronique de pinacol et un groupement triméthylsilyle a été développé afin d’accéder à des cyclopropanes gem-disubstitués. Les bases d’un procédé photochimique UV-visible utilisant ce nouveau réactif ont ensuite pu être établies. Ainsi, le premier exemple d’un gem-borocyclopropyl silane dérivé du styrène a pu être synthétisé. / This manuscript describes the work carried out in Pr. Charette’s laboratory between 2015 and 2019. It can be divided into two different topics: the development of new amidation strategies and the development of new cyclopropanation methodologies. Amide synthesis is still a challenge for the scientific community nowadays. Indeed, the development of simple, robust, atom economical and environmental friendly procedures remain one of the research priority in organic chemistry. To contribute to this field, an amide synthesis methodology has been developed by using diphenylsilane as a coupling reagent. The latter is commercially available, stable and cheap. Moreover, only a siloxane and dihydrogen are generated during the reaction. The developed methodology has also been applied to the synthesis of a series of di- and tripeptides. The cyclopropane moiety has been increasingly used in pharmaceuticals. Indeed, this moiety can influence different crucial parameters in the development of bioactive molecules. The development of new cyclopropanation methodologies is therefore a relevant field. Borocyclopropane synthesis is of particular interest: as a matter of fact, these compounds can create structural diversity via boronate functionalization. In order to obtain a user-friendly, robust and greener chemical process, a photochemical approach using continuous flow technology has been favored. A photoredox borocyclopropanation of styrenes has been developed; the latter is carried out under UV-A irradiation with xanthone as a photosensitizer. Mechanistic studies have supported that this transformation proceeds according to two concurrent photoredox catalytic cycles. Finally, a new diiodo reagent bearing a pinacol boronate group and a trimethylsilyl group has been developed to access gem-disubstituted cyclopropanes. The bases of a UV-visible photochemical process using this new reagent have then been established. Thereby, the first example of a gem-borocyclopropyl silane derived from styrene has been synthesized.

Self-assembly is ubiquitous in nature. A diverse range of materials with exceptional properties are accessed from a limited number of sub-units, through controlling structural order on all length-scales. Achieving the same level of control to access functional materials akin to those in nature is a key challenge in chemistry. Self-assembly of block copolymers (BCPs) offers a valuable bottom-up route, governed by non-covalent interactions, to access ordered assemblies on the nanoscale. Anisotropic nanostructures, such as one- and two-dimensional (1D and 2D) micelle morphologies, are of particular interest for various applications including those in biomedicine, catalysis, optoelectronics, and materials engineering. Crystallization-driven self-assembly (CDSA) of BCPs containing a crystallizable core-forming segment presents a robust route to preparing 1D and 2D micelles. Significantly, the use of pre-existing seed micelles in a process termed living CDSA allows access to 1D and 2D nanostructures of controlled size and low size-dispersity. Although CDSA protocols represent powerful tools for the formation controlled 1D and 2D nanostructures, key challenges associated with scale-up of these processes remain. In most cases, increasing the concentration at which living CDSA is performed results in competitive self-nucleation, compromising micelle size-control and dispersity. Living polymerization-induced crystallization-driven self-assembly (PI-CDSA) has been presented as a promising alternative route to accessing scalable 1D micelles. In this case, the polymerization, self-assembly, and seeded growth of a BCP containing a crystallizable core-forming segment occur in situ. However, the scope of living PI-CDSA is currently limited to the use of polyferrocenylsilane (PFS)-based BCPs. Owing to the diverse range of crystalline core chemistries compatible with CDSA protocols, and therefore various promising applications of 1D and 2D micelles, scale-up is essential to facilitate their further investigation and application. The work presented in this thesis focusses on upscaling the preparation and processing of controlled 1D and 2D micelles with a crystalline core. The scalable preparation of low dispersity 2D platelet micelles by living CDSA of a charge-terminated PFS homopolymer with surfactant counteranions is presented in Chapter 2. Here, fundamental insight into the effects of living CDSA concentration on platelet dimensions, structure fidelity, and aggregation behaviour is provided. In Chapter 3, the scope of living PI-CDSA is extended to access scalable length-controlled low dispersity 1D nanofibers containing a biodegradable poly(fluorenetrimethylenecarbonate) (PFTMC) crystalline core. PFTMC-based 1D fibers are of interest for biomedical applications, hence, in this work, it is demonstrated that living PI-CDSA can be used to prepare fibers exhibiting biologically-relevant lengths at scalable concentrations. In Chapter 4, the scalable formation of low dispersity 1D micelles by living CDSA of a PFS-based BCP in a continuous flow setup is explored. Processing of 1D micelles into microfibers using simple, low cost, and high throughput electrospinning techniques is demonstrated in Chapter 5. Finally, Chapter 6 summarises the contribution of this thesis to improving the scalability of CDSA protocols and provides future directions for this work. / Graduate / 2023-04-12

Les sulfilimines et sulfoximines sont des analogues monoazotés des sulfoxydes et des sulfones. Ces motifs ont récemment connu un regain d’intérêt considérable, notamment dû à leurs présences dans plusieurs molécules d’intérêt pour l’industrie pharmaceutique et pour l’agrochimie. Les travaux présentés dans ce manuscrit visent à développer de nouvelles stratégies de synthèse pour accéder à ces composés. Ces méthodes sont basées sur l’amination de thioéthers et de sulfoxydes via un intermédiaire nitrène métallique. Au cours des dernières années, notre groupe de recherche a mis au point un précurseur de nitrènes stable et facile à manipuler, les N-mésyloxycarbamates. Leur association avec des dimères de rhodium a permis de développer des réactions d’amination variées telles que l’insertion dans un lien C-H, l’aziridination de styrènes ou encore l’amination de thioéthers ou sulfoxydes pour former des sulfilimines et sulfoximines. Dans la perspective d’utiliser un métal de transition moins toxique et coûteux, il a été choisi d’étudier les complexes de fer. Dans un premier temps, une réaction d’amination photochimique de thioéthers en flux continu a été développée. Cette stratégie repose sur l’utilisation du Fe(acac)3 comme catalyseur et de la lumière UVA pour générer un nitrène métallique à partir de N-mésyloxycarbamates. Le choix d’un solvant biphasique constitué d’acétate d’éthyle et d’eau a permis de solubiliser le sous-produit de la réaction, à savoir le mésylate de sodium. Par la suite, une nouvelle méthode d’amination de thioéthers et de sulfoxydes, basée sur la formation in situ d’un complexe Fe butylimidazole a été mise au point. L’utilisation du butylimidazole comme base a permis d’obtenir des conditions homogènes grâce à la formation d’un liquide ionique comme sous-produit de la réaction. Cette méthodologie donne accès à plusieurs sulfilimines et sulfoximines avec d’excellents rendements, en batch ou en flux continu. Enfin, la réaction d’amination stéréosélective de thioéthers a été étudiée. Un système catalytique constitué d’un catalyseur de fer (II) et d’un ligand Pyox a permis d’obtenir des résultats prometteurs. / Sulfilimines and sulfoximines are aza-analogues of sulfoxides and sulfones. In recent years, these motifs have received considerable attention as they can be found in an array of biologically relevant molecules, including pharmaceuticals and agrochemicals. In the present thesis, we have developed new strategies to access these compounds. The methods are based on the amination of sulfides and sulfoxides via a metal nitrene species. Our research group has developed stable and easy to handle nitrene precursors, namely N-mesyloxycarbamates. We have performed various amination reactions such as C-H insertion, aziridination or sulfimidation in the presence of a rhodium dimer catalyst. As an alternative to rhodium, we have decided to study iron catalysts because of their low toxicity and wide availability. First, a photochemical amination reaction of sulfides was developed in continuous flow. The strategy relies on the use of Fe(acac)3 as a catalyst and UVA light to generate a metal nitrene from N-mesyloxycarbamates. A biphasic mixture was used as it allowed the solubilization of the by-product, namely sodium mesylate. Then, a novel amination reaction was also developed. The use of 1-butylimidazole as a base proved instrumental in enabling a homogenous reaction mixture. The methodology allowed the access to a wide range of sulfilimines and sulfoximines with excellent yields, in batch or in continuous flow. Finally, the stereoselective amination of thioanisole was studied. A catalytic system consisting of iron (II) catalyst and a Pyox ligand showed promising results.

[ES] El presente trabajo de investigación está centrado en la valorización y la mejora del bioetanol, empleando catalizadores heterogéneos, en un reactor de flujo continuo a escala de laboratorio. En primer lugar, en los laboratorios del Departamento de Química Industrial de la Universidad de Bolonia (Unibo), se ha estudiado la conversión catalítica del etanol en fase gaseosa sobre catalizadores basados en hidroxiapatitas (HAP). Los ensayos catalíticos se llevaron a cabo alimentando un reactor de lecho fijo a escala de laboratorio, empleando el catalizador en forma de pellets y una mezcla de etanol/He, en el rango de temperatura de 300-600 ºC. El interés se focalizó en la formación de productos de alta condensación, con el fin de obtener una mezcla orgánica que pueda ser empleada como bio-combustible. Tras seleccionar las condiciones de reacción, se sintetizaron y probaron diferentes hidroxiapatitas con capacidad de intercambio iónico que poseen metales de transición (Fe, Cu) y metales alcalinotérreos (Sr) en su composición. Mientras que las HAP conteniendo metales de transición actúan esencialmente como catalizadores ácidos, produciendo principalmente el producto de la deshidratación del etanol, el etileno, el catalizador de Sr-HAP permite la formación de una mezcla de reacción compleja, la cual necesita de una mayor optimización para cumplir con los requisitos adecuados para su posterior empleo como biofuel. A continuación, en los laboratorios del Instituto de Tecnología Química (ITQ) de la Universidad Politécnica de Valencia (UPV), el estudio se centró en dos materiales catalíticos diferentes, el óxido de zirconio y la sepiolita, una arcilla natural abundante en España. Ambos materiales se han probados para la transformación de etanol, en el rango de temperatura de 300-450 ºC, empleando un reactor de lecho fijo a escala laboratorio, con el catalizador en forma de pellets, y usando una mezcla de etanol/N2. Los catalizadores con óxido de zirconio se prepararon mediante dos métodos diferentes, precipitación e hidrotermal, variando algunos de los parámetros de síntesis (pH, naturaleza de la base), y empleando algunos metales de transición como elementos dopantes (Ti, Y). La presencia de un elemento dopante en la estructura de la zirconia favorece la estabilización de las fases tetragonal y cúbica frente a fase monoclínica. Todas las muestras exhibieron un comportamiento ácido. Resulta interesante que la zirconia dopada con 5%mol de Ti exhibe un comportamiento catalítico diferente, produciendo el dietiléter como principal producto a 300ºC, mientras que los otros catalizadores producen principalmente etileno, ambos, productos de la deshidratación del etanol. Por otra parte, se ha estudiado el efecto de las propiedades ácido-base de la sepiolita, modificada con metales alcalinos (Na, K, Cs) y cargas de metal variables (2, 4, 5, 7, 14 wt%), y de las propiedades redox de la sepiolita, como soporte de CuO o NiO, sobre la conversión catalítica de etanol a n-butanol. Las sepiolitas tratadas térmicamente actúan principalmente como catalizadores ácidos, produciendo preferentemente productos de deshidratación del etanol (etileno y dietiléter). Mientras que la presencia de un metal de transición no favorece la producción de n-butanol, la presencia de un metal alcalino en el sistema catalítico parece ser crucial para la formación de n-butanol. Los mejores resultados en términos de actividad (conversión de etanol, 59%) y selectividad (30%) de n-butanol se han obtenido a 400 ºC y un tiempo de contacto, W/F, de 2 g/mL·s, con el catalizador basado en sepiolita calcinada a 500 ºC, y modificada con 7 wt% de cesio, mediante impregnación en fase acuosa. / [CA] El present treball de recerca està centrat en la valorització i la millora del bioetanol, emprant catalitzadors heterogenis, en un reactor de flux continu a escala de laboratori. En primer lloc, en els laboratoris del Departament de Química Industrial de la Universitat de Bolonya (Unibo), s'ha estudiat la conversió catalítica de l'etanol en fase gasosa sobre catalitzadors basats en hidroxiapatitas (HAP). Els assajos catalítics es van dur a terme alimentant un reactor de llit fix, a escala de laboratori, contenint el catalitzador en forma de pèl·lets amb una mescla d'etanol/He, en el rang de temperatura de 300-600 °C. L'interés es va focalitzar en la formació de productes d'alta condensació, amb la finalitat d'obtindre una mescla orgànica que puga ser emprada com a bio-combustible. Després de seleccionar les condicions de reacció, es van sintetitzar i van provar diferents hidroxiapatitas amb capacitat d'intercanvi iònic que posseeixen metalls de transició (Fe, Cu) i metalls alcalinotérreos (Sr) en la seua composició. Mentre que les HAP contenint metalls de transició actuen essencialment com a catalitzadors àcids produint principalment el producte de la deshidratació de l'etanol, l'etilé, el catalitzador de Sr-HAP permet la formació d'una mescla de reacció complexa, la qual necessita d'una major optimització per a complir amb els requisits adequats per a la seua posterior ocupació com biofuel. A continuació, en els laboratoris de l'Institut de Tecnologia Química (ITQ) de la Universitat Politècnica de València (UPV), l'estudi es va centrar en dos materials catalítics diferents, l'òxid de zirconio i sepiolita, una argila natural abundant a Espanya. Tots dos materials s'han provats per a la transformació d'etanol en el rang de temperatura de 300-450 °C, emprant un reactor de llit fix a escala laboratori, contenint el catalitzador en forma de pèl·lets, i usant una mescla d'etanol/N2 Els catalitzadors amb òxid de zirconio es van preparar mitjançant dos mètodes diferents, precipitació i hidrotermal, variant alguns dels paràmetres de síntesis (pH, naturalesa de la base), i emprant alguns metalls de transició com a elements dopants (Ti, Y). La presència d'un element dopant en l'estructura de la zircònia afavoreix l'estabilització de les fases tetragonal i cúbica enfront de fase monoclínica Totes les mostres van exhibir un comportament àcid. Resulta interessant que la zircònia dopada amb 5%mol de Ti exhibisca un comportament catalític diferent, produint el dietiléter com a principal producte a 300 °C, mentre que les altres mostres produeixen principalment etilé, tots dos, productes de la deshidratació de l'etanol. D'altra banda s'ha estudiat l'efecte de les propietats àcid-base de la sepiolita, modificada amb metalls alcalins (Na, K, Cs) i càrregues de metall variables (2, 4, 5, 7, 14 wt%), i de les propietats redox de la sepiolita, com a suport de CuO o NiO, sobre la conversió catalítica d'etanol a n-butanol. Les sepiolites tractades tèrmicament actuen principalment com a catalitzadors àcids, produint principalment productes de deshidratació de l'etanol (etilé i dietiléter). Mentre que la presència d'un metall de transició no afavoreix la producció de n-butanol, la presència d'un metall alcalí en el sistema catalític sembla ser crucial per a la formació del n-butanol. Els millors resultats en termes d'activitat (conversió d'etanol, 59%) i selectivitat (30%) de n-butanol s'han obtingut a 400°C i un temps de contacte, W/F, de 2 g/ml·s amb el catalitzador compost de sepiolita calcinada a 500 °C, i modificada amb 7 wt% de Cs. / [EN] The present research work focused on the valorisation and upgrading of bio-ethanol over heterogeneous catalysts in a lab-scale continuous gas-flow system. Firstly, in the laboratories of the Department of Industrial Chemistry of the University of Bologna (Unibo), the catalytic ethanol gas-phase conversion was studied over hydroxyapatite (HAP) based catalysts. Catalytic tests have been carried out in the temperature range 300-600°C by feeding an ethanol/He mixture into a quartz lab-scale fixed bed reactor of pelletized catalyst. The focus was placed on enhancing the formation of higher condensation products in order to obtain an organic mixture with application as bio-fuel. After choosing the reaction conditions, ion-exchanged hydroxyapatite with transition metals (i.e., Fe, Cu) and alkaline earth metal (i.e., Sr) have been synthesized and tested. While the transition metal-exchanged HAP acted essentially as acid catalysts, yielding mainly the dehydration product of ethanol, ethylene, the Sr-HAP catalyst led to the formation of a complex reaction mixture the composition of which need further optimization in order to fill the requisite to be used as fuel-blend. Then, in the laboratories of the Institute of Chemical Technology (ITQ) of the Polytechnic University of Valencia (UPV), the study focused on two different catalytic materials, zirconium oxide and the natural clay sepiolite. Both the materials have been tested into the ethanol transformation carrying out the catalytic tests in the temperature range 300-450 °C by feeding an ethanol/N2 mixture into a quartz lab-scale fixed bed reactor of pelletized catalyst. Zirconium-oxide based catalysts have been prepared through two different methods, precipitation and hydrothermal, by varying some synthetic parameters (i.e., pH, the nature of the base) and by adding a transition metal as dopant agent (i.e., Ti and Y). The presence of a dopant into the zirconia structure favoured the stabilization of the tetragonal or cubic phase against the monoclinic one. All samples exhibited acidic behaviour. Interestingly, 5%mol Ti-doped zirconia exhibited a different catalytic behaviour yielding diethyl ether as major product at 300°C, while all the others samples produced mainly ethylene, both dehydration products of ethanol. The effect of acid-base properties of sepiolite, using alkali metals (i.e., Na, K, Cs) with different metal loading (i.e., 2, 4, 5, 7, 14 wt%) as promoters, and of the redox properties of sepiolite-supported CuO or NiO, on the catalytic conversion of ethanol into n-butanol has been investigated. Thermal treated sepiolite samples mainly acted as acid catalyst, yielding preferentially the dehydration products of ethanol (ethylene and diethyl ether). While the presence of a transition metal did not favour n-butanol production, the presence of an alkali metal into the catalytic system appeared to be crucial for n-butanol formation. Best results in terms of activity (ethanol conversion, 59%) and n-butanol selectivity (30%) where obtained at 400ºC and a contact time, W/F, of 2 g/mL·s over the catalyst consisting of sepiolite calcined at 500ºC modified with 7 wt% of cesium. / Balestra, G. (2022). Valorization of Bio-Alcohols into Added Value Chemicals [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/184991 / TESIS

For a business to maintain its competitiveness, it should adapt to the constantly changingmarket to be able to meet the needs and expectations of their customers for quality. Thiscan be done by working with quality development and process management. The goal ofthis work is to map processes for charging additional services at Postnord TPL, which isa leader in the Nordics in third-party logistics. Postnord TPL has had problems with thisprocess because it is considered time-consuming and often leads to errors in customerorder invoices since it is currently a very manual process. By mapping processes forcharging additional services, this study has succeeded in visualizing processes andidentifying areas for improvement. Based on the results from this study, an improvementproposal has since been drawn up and a new future process mapped out. The process forcharging additional services can be improved by implementing more automated ways ofworking that minimize the manual typing and transfer of information between differentExcel files. This would also improve communication and collaboration between theintake and administration departments. / För att en verksamhet ska kunna bevara sin konkurrenskraft bör den anpassa sig till denständigt förändrande marknaden för att kunna bemöta deras kunders behov ochförväntningar på kvalitet. Detta kan göras genom att arbeta med kvalitetsutveckling ochprocessledning. Målet med detta arbete var att kartlägga processen för debiteringar avtilläggstjänster hos Postnord TPL som är ledande i Norden inom tredjepartslogistik.Postnord TPL har haft problem med denna process eftersom den anses tidskrävande ochofta leder till att fel uppstår i kundorderfakturor på grund av att det i dagsläget är enväldigt manuell process. Genom att kartlägga processen för debiteringar avtilläggstjänster har man i denna studie lyckats visualisera processen och identifieraförbättringsområden. Utifrån resultaten från denna studie har sedan ettförbättringsförslag tagits fram och en ny framtida process kartlagts. Processen fördebiteringar av tilläggstjänster kan förbättras genom att implementera merautomatiserade arbetssätt som minimerar det manuella knappandet och överförandet avinformation mellan olika Excel filer. Detta skulle även förbättra kommunikationen ochsamarbetet mellan avdelningarna intag och administration.

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Användandet av deponier är en av de vanligaste metoderna för avfallshantering globalt. Trots insatser som gjordes för att förbjuda hushållsavfall i deponier under millennieskiftet, deponier skapade innan restriktionerna är fortfarande en risk för miljön. Under 2014 öppnade SÖRAB en kontinuerlig biologisk reningsanläggning (KBR-anläggning) på Löt Avfallsanläggning för att hantera lakvatten från en gammal deponi som under en tid fylldes med hushållsavfall. Sedan dess har SÖRAB arbetat med att förbättra KBR-anläggningen. Målet med denna studie är att utforma en driftstrategi för KBR-anläggningen för att förbättra kvävereningen vid låga temperaturer. Ett antal laborativa försök genomfördes, såsom den mikrobiella konsortiets livsduglighet i lakvattnet och tillväxten i både rumstemperatur och vid 4°C, bioaugmentation genom att berika den mikrobiella cellkulturen som redan finns i lakvattnet och hur detta förbättrar kvävereningen i jämförelse med tillsatser av den kommersiella bakterieblandningen ClearBlu Environmental och andra externa kolkällor. Resultaten från dessa laborativa försök påvisade komplett nitrifikation i både rumstemperatur och 4°C i berikat lakvatten från KBR-anläggningens L2A bassäng efter fem dagar. Försöket visade även på syresatt denitrifikation. Dessutom påvisades komplett denitrifikation inom fem dagar, vid rumstemperatur i lakvatten från anläggningens L2B bassäng. Under efterföljande pilotförsök påvisades möjligheten till upplivandet av den biologiska kvävereningen genom berikningen av den mikrobiella cellkulturen i lakvattnet. I ett pilotförsök då lakvatten från L2B bassängen berikades, komplett denitrifikation skedde under en anaerob fas på 16 dagar samt nitrifikation och aerob denitrifikation under ett påföljande 17 dagar lång aerob fas. Ett annat pilotförsök då lakvatten från L2A bassängen berikades påvisade både aerob och anaerob nitrifikation, då ammoniumrening skedde i både den syresatta och syrefria fasen. Tillsatsen av nutrient broth (näringsbuljong) kan påverka KBR-anläggningen, vilket kväver vidare studier. Resultatet från detta projekt tydligt påvisar att kvävereningen i KBR-anläggningen kan förbättras genom att berika den redan närvarande mikrobiella kulturen. / Landfilling has been one of the most popular methods of handling waste globally. Despite the efforts made to stop the disposal of household waste during the turn of the millennia, the landfills formed before these restrictions are still at risk for causing harm to the environment. In 2014, SÖRAB opened a continuous-flow biological treatment (KBR) facility in Löt to treat the leachate produced in one of their older landfills, once filled with household waste. Since then, SÖRAB has been working on improving the treatment facility. The aim of this the study is to find a suitable process to enhance the nitrogen removal at low temperature. Several laboratory scale experiments were performed, such as viability of microbial consortia in the leachate and growth at room temperature and at 4°C, testing bioaugmentation by enriching the microbial cell culture in the leachate and their efficiency in removing nitrogen, compared to the commercial cell culture ClearBlu Environmental and carbon source addition. The results displayed complete nitrification at both room temperature and 4°C in bioaugmented, enriched leachate originating from the L2A basin of the KBR facility, after five days. These trials also suggested the occurrence of aerated denitrification. Complete denitrification within five days was seen at room temperature in bioaugmented, enriched leachate from the L2B basin of the same facility. The ensuing pilot scale trials proved the possibility to revive the biological nitrogen removal by microbial cell culture enrichment. In one pilot in which leachate from the L2B basin was enriched, complete denitrification in the anaerobic phase consisting of 16 days occurred, along with some nitrification and aerated denitrification in the 17 day long aerated phase that followed. Another pilot scale trail in which leachate from the L2A basin was enriched, both aerobic and anaerobic nitrification occurred, as ammonium removal occurred in both the aerated and unaerated phases. The addition of nutrient broth might influence the KBR system which needs further study. The results from this project clearly demonstrate that nitrogen removal in the KBR facility could be enhanced using a culture naturally present in the facility.

Enhanced biological phosphorus removal (EBPR) was researched from the performance of a modified University of Cape Town (UCT), anaerobic-anoxic/nitrifying-aerobic process. The work focussed on high P influent where milk was compared to carbohydrates as exogenous added carbon and typical settled sewage. The results confirmed that at equal COD load in the influent (minimum COD:P (250:5) ratio for EBPR), milk always provided sufficient soluble substrate than the carbohydrate mix, but also improved the EBPR performance. The laboratory scale treated 10L/day where 2 parallel treatment trains for milk and an equivalent carbohydrate mix as supplement to compare and study the P sequestration from hypothesised P ligands in milk and easily assimilable carbon (AOM) after fermentation for biological P uptake. The aerobic bioreactors used submerged flat sheet membranes (AeMBR) to improve the effluent quality and reduce the suspended solid residues. The results suggested extra benefits from adding calcium chloride (CaCl2) (200 ml at 250 mM/day or 200 mg/L treated) to form P complexes both in the anaerobic and aerobic zones (100 ml CaCl2 250mM/zone/day). To complete P removal a calcium phosphate (CaPO4) further treatment stage (post membrane final effluent (F.E.)) was added for nucleation. The combination of, A2O-N, exogenous carbon and calcium addition improved the performance of the EBPR, and enabled the laboratory units to achieve less than the 1 mg/L P required by the EU Directive. The process was tested at higher than normal P loads (maximum 100 mg/L) (domestic wastewater influent 15 mg/L). Experiments with influent P load ≤ 50mg/L, with 1% milk as AOM were compared to the carbohydrate mix and could remove soluble P to less than 1mg/L above 97% and less than 2 mg/L more than 99% of the in the time respectively. With an influent P load of 60mg/L (maximum 100 mg/L), the soluble P in the F.E. with milk was below 5 mg/L and below 8 mg/L with carbohydrates mix. The results showed that most of the phosphorus was retained by the sludge during the anoxic-aerobic phases. The remaining phosphate in the F.E. was able to pass through AeMBR pore size (0.4 μm) and needed to be chelated by the nucleation process. The results indicated this A2O-N modifications achieved stable nutrient removal and also offered the potential for more sustainable phosphorus recovery. The EBPR without AOM was 25% less efficient compared to milk and never achieved the E.U standard of 1mg/L in final effluent. The flat sheet membrane always achieved a NTU final effluent below 1 and the TOC always greater than 90% removal or less than the EU 125 standard regardless of the feeding COD/P ratio.

Articular cartilage has a low propensity for self-repair, due to which 27 million people are affected by osteoarthritis every year in North America. The current repair techniques used for cartilage defects possess flaws that reduce long-term clinical success. Tissue engineering carries with it the promise of engineering hyaline-like cartilage with physical and biochemical properties, similar to that of native cartilage. This being said, the primary objective of my project was to engineer clinically relevant sized articular cartilage constructs. To achieve my objective, first, I investigated the effect of continuous culture on cartilaginous tissue growth. Constructs grown under continuous media flow significantly accumulated more collagen and glycosaminoglycan, and displayed a stratified morphology, similar to that found in native cartilage. The second goal was to further increase chondrocyte proliferation, and extracellular matrix (ECM) accumulation. To achieve this, constructs were grown in a bioreactor with media supplemented with 14 mM sodium bicarbonate (NaHCO3). Constructs cultivated in the bioreactor with NaHCO3 supplementation exhibited a significant (p<0.05) increase in ECM accumulation (a 98-fold increase in glycosaminoglycans and a 25-fold increase in collagen content), cell proliferation (a 13-fold increase), and thickness (a 28-fold increase) compared to all other conditions (static and reactor without NaHCO3 supplementation). The third goal was to engineer cartilage constructs with as little cells as possible, reducing donor site morbidity. From the results obtained, it was evident that the monolayer constructs outperformed all the other constructs (pellet, biopsy, and minced). The final goal was to understand the underlying reason for the increased proliferation. First, I investigated if there were any differences present in intracellular pH (pHi) and intracellular buffering capacity. Second, I determined the role of extracellular pH (pHe) on cell proliferation. In an effort to accurately achieve this, I, for the first time, have reported on measuring pHi of chondrocytes while still in culture (2D and 3D cultures) using a confocal microscope. This study demonstrated the importance of extracellular environments, such as pHe, extracellular buffering capacity, and the presence of carbon dioxide and bicarbonate ions for chondrocyte proliferation. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2012-10-30 19:19:32.026