Esta tese esta dividida em três capítulos: Primeiro capítulo -­ Resolução cinética enzimática de sulfetos, selenetos e teluretos em CO2 supercrítico. Inicialmente, a estabilidade dos β-hidróxi organocalcogenetos foi avaliada em CO2 supercrítico. Como a variação da pressão e temperatura afeta a densidade do fluído de forma não linear, um estudo sistemático foi realizado para avaliação desses parâmetros, visando altos excessos enantioméricos para os β-­hidróxi-­ sulfetos e -­selenetos, os quais foram determinados por cromatografia líquida de alta eficiência (CLAE). Os β-­hidróxi-­teluretos não se apresentaram estáveis sob as mesmas condições. Desta maneira, um novo método para determinar o excesso enantiomérico dos β-­hidróxi-­teluretos foi desenvolvido, utilizando RMN de 125Te. Capítulo 2 -­ Utilização de teluroferrocenos quirais como sondas quirais para a determinação de excessos enantioméricos usando RMN de 125Te. Teluroferrocenos quirais, substituídos por grupos amidas, oxazolinas e aminas foram preparados. Tais moléculas contendo telúrio interagem com amostras quirais, formando complexos diastereoisoméricos, nos quais os átomos de telúrio são submetidos a diferentes ambientes químicos, o que resulta em diferentes deslocamentos químicos para cada complexo diastereoisomérico. A integração dos sinais de 125Te permite a determinação do excesso enantiomérico de amostras quirais. Terceiro capítulo - Calcogenação de olefinas ativadas. Organocalcogenolatos de lítio gerados in situ reagiram com olefinas ativadas. Na presença de uma fonte de prótons, foram formados os calcogenetos β-­funcionalizados. Em meio anidro, o enolato intermediário pode ser capturado com compostos carbonílicos em reações tandem tri-­ componentes, gerando precursores de Morita-­Baylis-­Hillman, quando Y = S, Se. / This thesis contains three chapters: 1st chapter - Kinetic enzymatic resolution of sulfides, selenides and tellurides in supercritical CO2. Initialy, the stability of the β-­hydroxy organochalcogenides in suprecritical CO2 was evaluated. As the variation in the pressure and temperature affect the fluid density in a non-­linear way, a systematic study on the influence of these parameters was performed, aiming a high enantiomeric excess for the products. The enantiomeric excesses of the β-­hydroxy sulfides and selenides were determined by high performance chiral liquid chromatography (HPLC). The β-­hydroxy tellurides were not stable under the same conditions. In view of this fact, a new method to determine the enantiomeric excess of the β-­hydroxy tellurides was developed, using 125Te NMR spectroscopy for this end. 2nd chapter - Use of chiral telluroferrocenes as chiral probes for the enantiomeric excess determination using 125Te NMR spectroscopy. Chiral telluroferrocenes, substituted by amides, oxazolines and amines were prepared. These chiral tellurium containing molecules interact with chiral samples, forming diastereomeric transient complexes in which the tellurium atoms are submitted to different chemical environments, what leads to different 125Te chemical shifts for each diastereomeric complex integration of the 125Te NMR spectra allowing the determination of the enantiomeric excess of the chiral samples. 3rd chapter - Chalcogenation of activated olefines. In situ gererated lithium organochalcogenolates were reacted with activated olefines. In the presence of a proton source, the β-functionalized chalcogenides were formed. Under anhydrous conditions, the intermediate enolate can be trapped with carbonyl compounds in a three components process to give precursors of Morita-­Baylis-­Hillman adducts when Y = S, Se.

A descoberta de petróleo na camada de Pré-Sal possibilita a geração de ganhos em relação à dependência energética do país, mas também grandes desafios econômicos e tecnológicos. Os custos de extração são maiores devido a vários fatores como a exigência de equipamentos de exploração que suportem elevadas pressões, altas temperaturas e grandes concentrações de gases ácidos, tais quais, dióxido de carbono (CO2) e sulfeto de hidrogênio (H2S). Uma das principais preocupações com o CO2 é evitar liberá-lo para a atmosfera durante a produção. Com a modelagem termodinâmica de dados de equilíbrio de sistemas envolvendo CO2 supercrítico e hidrocarbonetos é possível projetar equipamentos utilizados em processos de separação. A principal motivação do trabalho é o levantamento de dados de equilíbrio de fases de sistemas compostos de CO2 e hidrocarbonetos, possibilitando assim prever o comportamento dessas misturas. Os objetivos específicos são a avaliação do procedimento experimental, a estimação e predição dos parâmetros de interação binários para assim prever o comportamento de fases dos sistemas ternários envolvendo CO2 e hidrocarbonetos. Duas metodologias foram utilizadas para obtenção dos dados de equilíbrio: método estático sintético (visual) e método dinâmico analítico (recirculação das fases). Os sistemas avaliados foram: CO2 + n-hexano, CO2 + tetralina, CO2 + n-hexadecano, CO2 + n-hexano + tetralina e CO2 + tetralina + n-hexadecano à alta pressão; tetralina + n-hexadecano à baixa pressão. Para o tratamento dos dados foi utilizada equação de estado cúbica de Peng-Robinson e a regra de mistura clássica / The discovery of oil in the pre-salt layer enables the generation of earnings in relation to the energy dependence of the country, but also large economic and technological challenges. Extraction costs are higher due to various factors such as the demand for mining equipment capable of withstanding high pressures, high temperatures and high concentrations of acid gases, as such, carbon dioxide (CO2) and hydrogen sulfide (H2S). A major concern with CO2 is to avoid releasing it into the atmosphere during production. With the thermodynamic equilibrium modeling systems involving data supercritical CO2 and hydrocarbon is possible to design equipment used in separation processes. The main motivation is the data collection phase equilibrium compounds CO2 systems and hydrocarbons, thus enabling predict the behavior of these mixtures. The specific objectives are to assess the experimental procedure, the estimation and prediction of binary interaction parameters so as to predict the behavior of phases of ternary systems involving CO2 and hydrocarbons. Two methodologies were used to obtain the equilibrium data: synthetic static method (visual) and analytical dynamic method (recycling phase). The systems were evaluated: CO2 + n-hexane, CO2 + tetralin, CO2 + n-hexadecane, CO2 + n-hexane + tetralin, and CO2 + tetralin + n-hexadecane at high pressure; tetralin + n-hexadecane at low pressure. For the treatment of the data was used cubic equation of state of Peng-Robinson and the classical mixing rule

Cette thèse évalue d'abord le potentiel thermodynamique du cycle au CO2 supercritique (sc-CO2) pour une large gamme de température de source chaude et étudie son couplage aux applications nucléaires, 45.7% d’efficacité thermique étant obtenu pour un réacteur à neutrons rapides refroidi au sodium. Des simulations CFD sont réalisées sur un compresseur à échelle réduite et confrontées à une expérience, apportant des éléments de qualification. Des simulations sur un compresseur à échelle 1:1 révèlent des particularités liées à la compression du sc-CO2 au comportement gaz réel, offrant un retour d’expérience pour la conception. Dans ce cadre, une approche de cartes de performance est proposée et validée à l'aide de simulations. Enfin, une étude de la collapse d’une bulle dans le CO2 liquide au voisinage du point critique est réalisée et indique l'absence d’effet destructif de cavitation, ouvrant la voie au fonctionnement du compresseur en phase liquide, lieu optimum de l'efficacité du cycle. / This study first evaluates the thermodynamic performance of the supercritical CO2 (sc-CO2) cycle in a large range of heat source temperature, with a focus on the nuclear applications; a thermal efficiency of 45.7% is reported for a Sodium-cooled Fast Reactor. Second, CFD simulations have been performed on a small scale sc-CO2 compressor and results have been confronted positively with the experimental data. Simulation results on a real scale compressor have then revealed some particularities during the compression of a real fluid, providing feedbacks for the component design. In addition, a reliable performance maps approach has been proposed for the sc-CO2 compressor and validated using the CFD results. Finally, an investigation of bubble collapse in the liquid CO2 near the critical point has disclosed the likely absence of detrimental effects. As such, risks of cavitation damage should be low, favoring the compressor operation in the liquid region for cycle efficiency improvement.

Thesis (PhD (Chemical Engineering))--Cape Peninsula University of Technology, 2020 / The use of bioproducts in different commercial sectors such as medicine, agriculture, cosmetics, food, and chemical industries motivates the need for easy production and recovery techniques of bioproducts at laboratory and pilot scale. This study aims at the production and recovery of some selected bioproducts using supercritical fluid extraction techniques. Three products are chosen as case studies: these are ethanol, acetoin, and vanillin, since the ease of separation is influenced by the concentration of the product in the broth, these compounds were selected based on their concentration in the fermentation broth, according to literature sources. A standard method was developed in a spectrophotometer for quantifying the targeted product in the broth, while the product recovery studies was carried out using a supercritical fluid extraction pilot plant. Saccharomyces and Bacillus species were chosen for the bioproduction of the selected bioproducts. Experimental design and statistical analysis of results were carried out using response surface methodology (RSM) and artificial neural network (ANN). Studies on each of the selected bioproducts are as justified in the paragraphs below. Bioethanol production has recently become an increasing trend in research, with a focus on increasing its economic viability. Hence, the need to develop a low-cost fermentation medium with minimum redundant nutritional supplements, thereby minimizing the costs associated with nutritional supplements whereby inoculum preparation becomes necessary for ethanol production. Corn steep liquor (CSL) in glucose fermentation by Saccharomyces Type 1 (ST1) strain and Anchor Instant Yeast (AIY), which are low-cost media, are used as replacements for yeast extract (YE). The fermentation process parameters were optimized using artificial neural networks (ANN) and the response surface methodology (RSM). The study shows that for CSL, a maximum average ethanol concentration of 41.92 and 45.16 g/L representing 82% and 88% of the theoretical yield were obtained after 36 h of fermentation in a shake flask for ST1 and AIY respectively. For YE, ethanol concentration equivalent to 86% and 88% of theoretical yield were obtained with ST1 and AIY respectively after 48 h. Although, ANN predicted the responses of ethanol yield better than RSM, optimum conditions for ethanol production were better predicted by RSM. The consumers’ preference for ‘naturally’ produced aromas drives the development of bioproduction of acetoin from glucose with a view to optimize its production. The results revealed that by using a cheap nitrogen source, corn steep liquor, the yield of acetoin was similar to those of yeast and beef extracts. Furthermore, it was shown that by using Box-Behnken design, the optimum parameters such as glucose concentration, corn steep liquor, and inoculum size to maximize the concentration of acetoin produced were 78.40 g/L, 15.00% w/v and 2.70% v/v respectively. The validated concentration of acetoin produced in a triplicate analysis, 10.7 g/L, was 0.06% less than the predicted value. Increasing awareness of consumers of healthy, eco-friendly flavors and fragrances motivates the bioproduction of vanillin. The interactive effects of three variables on vanillin yield were evaluated by response surface methodology (RSM) with Box-Behnken design (BBD) model. The results showed the optimum conditions for the biotransformation of ferulic acid into vanillin can be achieved with maximum overall desirability (D) of 1.0 and a significant (p<0.05) quadratic model with regression coefficient (R2) of 0.995. Corn steep liquor, initial ferulic acid concentration and pH significantly influence the concentration of vanillin in the broth. The results in triplicate experiments confirmed vanillin yield of 386 mg/L after validation, which was in agreement with the prediction of the model. The maximum vanillin yield of 384.40 mg/L was predicted when corn steep liquor, ferulic acid concentration and pH were 7.72 g/L, 2.33 g/L, and 9.34 respectively. Fermentation system in a bioreactor has been proven to be an efficient system for the study of controlled fermentation variables when compared to a shake flask study. The influence of agitation, aeration, time and pH were analysed by Taguchi orthogonal array design for the upscale of acetoin in a bioreactor. The optimized parameters in 1.3L of fermentation vessel were as follows: 300 rpm agitation, 1.5 slpm aeration; 2 days’ fermentation time and 6.5 pH value. Agitation with above 70% was the most contributing factor and other variables were less than 30% in the percentage analysis of variance of each fermentation variables in the batch study of acetoin. A fourfold gain in acetoin titre (42.30 g/L) was obtained with the same substrate concentration in a lab-scale bioreactor on scaling up when compared with the shake flask batch study. The validated acetoin concentration of 41.72 g/L was obtained after a triplicate experiment to confirm the possibility of reproducing acetoin using the optimized conditions. Many separation techniques have been proven to recover value-added products from fermentation broth with a preference for several methods above other and new techniques that are emerging. Supercritical fluids separation using CO2 is one such technique. The feasibility of acetoin concentration and recovery was studied in supercritical CO2 pilot plant with pressure ranges of 100 to 300 bar, CO2 feed rate of 5 to 15 kg/h, at a process temperature of 37 and 80 °C in simulated and fermentation broth, respectively. The validated conditions for the fractionation of acetoin by supercritical fluid extraction (SFE) were determined as follows: extraction pressure, 300 bar; CO2 feed rate, 15 kg/h; extraction temperature 37 °C; and fractionation time of 30 minutes. At these operating conditions, the percentage recovery of acetoin with respect to the feed solution at the raffinate for the simulated and actual ermentation broth was 77.8% (0.20 g/L) and 77% (0.15 g/L) respectively. A two-fold extract increase was obtained after 30 minutes of fractionation. The study provides the technical feasibility and the base case data which are critical to the development and design of processes for production and recovery of acetoin. The lesson gleaned from this study may be extended to develop processes for the production and recovery of other bioproducts (ethanol and vanillin).

En raison de leurs excellentes propriétés, les polyoléfines telles que le polypropylène et le polyéthylène sont largement utilisées dans des applications d'emballage alimentaire. Cependant, tout au long de leur cycle de vie ou de la première utilisation, les polyoléfines peuvent être exposées à des milieux contaminés qui limitent leur recyclabilité en contact alimentaire. Par conséquence, le recyclage de polyoléfines au contact alimentaire nécessite des niveaux de décontamination rigoureux et donc une technologie de décontamination avancée. L’objectif de ce travail consiste dans un premier temps à étudier la faisabilité et la potentialité de l’extraction par CO2 supercritique en mode batch pour la purification de polyoléfines (extraction d’additifs et de contaminants modèles). On s’est plus particulièrement attaché à étudier l’effet des paramètres du procédé sur la cinétique de l’extraction ainsi que l’influence de l’extraction supercritique sur les comportements rhéologique et thermique des matériaux purifiés. Dans un deuxième temps, on s’est intéressé au développement d’un nouveau procédé continu d’extraction par couplage de l’extraction supercritique et l’extrusion bi-vis. Les résultats les plus importants ont montré la potentialité de l’extraction par CO2 supercritique en mode batch pour la purification de polyoléfines sans influencer significativement les propriétés de la matrice / Due to their excellent properties, polyolefins such as polypropylene and polyethylene are widely used in food packaging applications to preserve and protect foodstuffs. However, throughout their lifecycle or first use, polyolefins can be exposed to contaminated media which limit their recyclability in food contact applications. Therefore, the recycling of polyolefins into direct food contact applications requires rigorous decontamination levels and thus effective and advanced recycling technology. The objective of this work is, at first hand, to study the feasibility and the potential of supercritical CO2 extraction in batch process for the purification of polyolefins (extraction of additives and model contaminants). In the whole, we investigated the effects of process parameters and contaminant structure on the extraction kinetic, and the influence of the supercritical CO2 extraction on the rheological and thermal behaviors of the purified materials. On the other hand, we aimed at the development of a novel continuous extraction process by coupling supercritical extraction technique and twin-screw extrusion. The most significant results showed the potential of supercritical CO2 extraction in batch mode for the purification of polyolefins without influence significantly the matrix properties

One of the key challenges the world will need to face during the 21st century is global warming and the consequent climate change. Its presence is indisputable, and decarbonizing the gird emerges as one of the required pathways to achieve global sustainable objectives. Solar energy power plants have the potential to revert this situation and solve the problem. One way to harness this energy is through Concentrated Solar Power plants. The major advantage and potential of this technology is its ability to integrate cost-effective Thermal Energy Storage (TES), which is key with such an inherently intermittent resource. On the other hand, the drawback is the high current Levelized Cost of Energy (LCOE). The other main way to harness that highlighted solar energy is the use of Photovoltaic panels, which have recently achieved very competitive LCOE values. On the other hand, the storage integration is still a very pricey option, normally done with Battery Energy Storage Systems (BESS). As a conclusion, a hybrid power plant combining the LCOE of the PV and the TES of the CSP emerges as the key way of achieving a very competitive solution with a big potential. This master thesis aims at exploring the possibilities of a hybrid CSP and PV power plant with a sCO2 power cycle, integrated in the primary, secondary and tertiary electricity markets. To achieve this purpose, firstly, a Python-based Energy Dispatcher was developed to control the hybrid power plant. Indeed, the Dispatcher is the tool that decides when to produce, when to store… following an optimization problem. This can be formulated mathematically, and that was done and integrated into the Python code using Pyomo, a software for optimization problems. As a result, the Dispatcher achieved an effective control of the plant, showing intelligent decisions in detailed hourly analyses. The results were very promising and included optimization functions as maximizing the profitability of the plant or the total production, among others. To proceed with the Techno-economic assessment of the hybrid plant, the electricity markets were studied. The main source of income of any power plant is normally the revenue from selling electricity to the grid, but since there are several markets, there are also other possibilities. In this thesis, it was assessed from a Techno-Economic perspective how the performance and optimal design of the plants vary when providing different services extra to selling electricity to the grid. The conclusion was that even though the Net Present Value (NPV) achieved working on the spot market was already very high, the extra value added from participating in the secondary or tertiary markets was indisputable. Indeed, the profits attained in those markets were between two and four times higher than the ones of the spot market. This is a specific case, but a trend was identified: these hybrid power plants have a huge possibility and a bright future on the service markets. As a consequence, this thesis shows the huge potential of hybrid power plants integrated in the grid participating in several markets. It also lays the foundation for future studies in other locations, under different conditions and with different technologies, among others.

Tesis por compendio / [ES] Generalmente, se utilizan tratamientos térmicos para la esterilización de emulsiones. Sin embargo, el calentamiento ha demostrado inducir la hidrólisis de lípidos y lecitina. En este sentido, las tecnologías no térmicas están surgiendo en la industria para alcanzar la estabilidad microbiana evitando la pérdida de calidad relacionada con el calor. El CO2 supercrítico (SC-CO2) y los campos eléctricos pulsados (PEF) son tecnologías no térmicas para la inactivación microbiana. Sin embargo, estas técnicas en ocasiones requieren altas intensidades o tiempos de tratamiento largos para garantizar la seguridad del producto. La literatura ha demostrado la capacidad de los ultrasonidos de alta potencia (HPU) para intensificar fenómenos de transferencia de masa y calor. Por lo tanto, su aplicación a tecnologías no térmicas podría ser un enfoque interesante para mejorar la efectividad de la inactivación microbiana. En este contexto, el objetivo fue evaluar el efecto de los tratamientos SC-CO2, PEF y HPU, aplicados de forma individual y combinada, sobre la inactivación de diferentes microorganismos en emulsiones. Para ello, por un lado, se estudió el efecto de la aplicación de HPU a los tratamientos SC-CO2 sobre diferentes tipos de microorganismos y sobre medios con diferente contenido en aceite. Por otro lado, se evaluó el efecto de los tratamientos PEF y HPU individuales y combinados sobre diferentes microorganismos Los resultados mostraron que, en general, la aplicación de HPU intensificó la capacidad de inactivación de SC-CO2. Los HPU probablemente facilitaron la solubilidad del CO2 en el medio y provocaron daños en las células. En este sentido, el análisis microscópico de las células inactivadas reveló importantes cambios morfológicos, incluyendo paredes celulares dañadas y pérdida del contenido citoplasmático. En cambio, los HPU no mejoraron la inactivación de SC-CO2 de las esporas de A. niger en emulsión. El aumento de la presión llevó a una mayor inactivación, a excepción de E. coli en agua, donde no se encontró efecto de la presión. Sin embargo, las presiones por encima de 350 bar no parecen ejercer ninguna inactivación adicional. El aumento de temperatura tuvo un efecto significativo para todos los tratamientos y microorganismos. En cuanto al efecto del medio, se sabe que la presencia de aceite protege a los microorganismos, como se observó en la inactivación de bacterias SC-CO2 en agua y en emulsiones con diferente contenido en aceite. Sin embargo, la aplicación de HPU enmascaró el efecto protector que ejerce el aceite en las emulsiones. En cambio, para las esporas de A. niger no se encontró efecto del medio sobre la efectividad de los tratamientos. En relación al efecto de los tratamientos de SC-CO2 + HPU sobre la calidad de las emulsiones, se encontró un efecto leve de las condiciones del proceso y mediante la selección de condiciones adecuadas de SC-CO2 + HPU, se pudieron obtener cambios mínimos en la calidad de las emulsiones y una inactivación satisfactoria de todos los microorganismos, excepto para las esporas de G. stearothermophilus. Con respecto a los tratamientos de PEF y HPU, no se logró la inactivación completa de las emulsiones con los tratamientos individuales. Sin embargo, cuando el PEF (152,3-176,3 kJ / kg) fue seguido de HPU (3 min), se obtuvieron niveles de inactivación de 8,2, 6,6 y 1,0 ciclos-log para E. coli, A. niger y B. pumilus. Además, la inactivación lograda por el tratamiento con PEF-HPU fue mayor que la de la suma de los tratamientos individuales para todos los microorganismos. Por el contrario, la inactivación lograda por el tratamiento HPU-PEF fue menor que la de la suma de los tratamientos individuales. Por lo tanto, la secuencia más eficaz fue aquella en la que el PEF fue seguido de los HPU. Se puede concluir que, la combinación de HPU con SC-CO2 o PEF generalmente mejoró la inactivación microbiana. En consecuencia, se podrían utili / [CA] Generalment, s'utilitzen tractaments tèrmics per a l'esterilització d'emulsions. No obstant això, el calfament ha demostrat induir la hidròlisi de lípids i lecitina. En aquest sentit, les tecnologies no tèrmiques estan sorgint en la indústria per a aconseguir l'estabilitat microbiana evitant la pèrdua de qualitat relacionada amb la calor. El CO¿ supercrític (SC-CO¿) i els camps elèctrics premuts (PEF) són tecnologies no tèrmiques per a la inactivació microbiana. No obstant això, aquestes tècniques a vegades requereixen altes intensitats o temps de tractament llargs per a garantir la seguretat del producte. La literatura ha demostrat la capacitat dels ultrasons d'alta potència (HPU) per a intensificar fenòmens de transferència de massa i calor. Per tant, la seua aplicació a tecnologies no tèrmiques podria ser un enfocament interessant per a millorar l'efectivitat de la inactivació microbiana. En aquest context, l'objectiu va ser avaluar l'efecte dels tractaments SC-CO¿, PEF i HPU, aplicats de manera individual i combinada, sobre la inactivació de diferents microorganismes en emulsions. Per a això, d'una banda, es va estudiar l'efecte de l'aplicació de HPU als tractaments SC-CO¿ sobre diferents tipus de microorganismes i sobre mitjans amb diferent contingut en oli. D'altra banda, es va avaluar l'efecte dels tractaments PEF i HPU individuals i combinats sobre diferents microorganismes Els resultats van mostrar que, en general, l'aplicació de HPU va intensificar la capacitat d'inactivació de SC-CO2. Els HPU probablement van facilitar la solubilitat del CO¿ en el mitjà i van provocar danys en les cèl·lules. En aquest sentit, l'anàlisi microscòpica de les cèl·lules inactivades va revelar importants canvis morfològics, incloent parets cel·lulars danyades i pèrdua del contingut citoplasmàtic. En canvi, els HPU no van millorar la inactivació de SC-CO2 de les espores de A. niger en emulsió. L'augment de la pressió va portar a una major inactivació, a excepció d'E. coli en aigua, on no es va trobar efecte de la pressió. No obstant això, les pressions per damunt de 350 bar no semblen exercir cap inactivació addicional. L'augment de temperatura va tindre un efecte significatiu per a tots els tractaments i microorganismes. Quant a l'efecte del medi, se sap que la presència d'oli protegeix els microorganismes, com es va observar en la inactivació de bacteris SC-CO¿ en aigua i en emulsions amb diferent contingut en oli. No obstant això, l'aplicació de HPU va emmascarar l'efecte protector que exerceix l'oli en les emulsions. En canvi, per a les espores de A. niger no es va trobar efecte del medi sobre l'efectivitat dels tractaments. En relació a aquest efecte dels tractaments de SC-CO2 + HPU sobre la qualitat de les emulsions, es va trobar un efecte lleu de les condicions del procés i mitjançant la selecció de condicions adequades de SC-CO2 + HPU, es van poder obtindre canvis mínims en la qualitat de les emulsions i una inactivació satisfactòria de tots els microorganismes, excepte per a les espores de G. stearothermophilus. Respecte als tractaments de PEF i HPU, no es va aconseguir la inactivació completa de les emulsions amb els tractaments individuals. No obstant això, quan el PEF (152,3-176,3 kJ / kg) va ser seguit de HPU (3 min), es van obtindre nivells d'inactivació de 8,2, 6,6 i 1,0 cicles- log per a E. coli, A. niger i B. pumilus. A més, la inactivació reeixida pel tractament amb PEF- HPU va ser major que la de la suma dels tractaments individuals per a tots els microorganismes. Per contra, la inactivació reeixida pel tractament HPU- PEF va ser menor que la de la suma dels tractaments individuals. Per tant, la seqüència més eficaç va ser aquella en la qual el PEF va ser seguit dels HPU. Es pot concloure que, la combinació de HPU amb SC-CO¿ o PEF generalment va millorar la inactivació microbiana. En conseqüència, es podrien utilitzar temps de / [EN] Thermal treatments are generally used for the sterilization of emulsions. However, heating has demonstrated its ability to induce the hydrolysis of lipids and lecithin. In this sense, non-thermal technologies are emerging in the industry with the aim of achieving microbial stability while avoiding the loss of quality related to heat. Supercritical carbon dioxide (SC-CO2) and pulsed electric fields (PEF) are non-thermal technologies for microbial inactivation. However, these techniques have demonstrated to require high treatment intensities or long treatment times to guarantee the product's safety. Therefore, there is still room for the improvement in the use of these technologies. Literature has illustrated the capacity of high power ultrasound (HPU) for the intensification of mass and/or heat transfer phenomena. Therefore, its application to non-thermal technologies could be an interesting approach to enhance the microbial inactivation effectiveness. In this context, the objective was to evaluate the effect of SC-CO2, PEF and HPU treatments, applied in individual and combined form, on the inactivation of different microorganisms in emulsions. In order to achieve this goal, on the one hand, the influence of the implementation of HPU to the SC-CO2 treatments was studied on different types of microorganisms and on media with different oil content. On the other hand, the effect of the individual and combined PEF and HPU treatments was assessed on different microorganisms. Results showed that, generally, the application of HPU intensified the inactivation capacity of SC-CO2. HPU probably enhanced the solubilization of CO2 into the medium and provoked damages in the cells. In this regard, the microscopy analysis of the inactivated cells revealed important morphological changes, including damaged cell walls and an important loss of the cytoplasmic content. Nevertheless, HPU did not improved the SC-CO2 inactivation of A. niger spores in emulsion. The increase of the pressure led to a higher inactivation, except for E. coli in water, where no effect of pressure was found. However, pressures above 350 bar did not seem to exert any additional inactivation. The increase of the temperature had a significant effect for all treatments and microorganisms. Regarding the effect of the medium, the presence of oil is known to protect microorganisms, as was observed in the SC-CO2 inactivation of bacteria in water and in emulsions with different oil content. However, the application of HPU masked the protective effect exerted by the oil in the emulsions. On the contrary, for A. niger spores no effect of the media was found on the effectiveness of the treatments In relation to the effect of the SC-CO2 + HPU treatments on the quality of the treated emulsions, only a mild effect of the process conditions was found and by the selection of suitable SC-CO2 + HPU conditions, minimal changes on the quality of the emulsions and a satisfactory inactivation for all the microorganisms, except for G. stearothermophilus spores, can be obtained. Regarding PEF and HPU treatments, the complete inactivation in the emulsions was not achieved with the individual treatments. However, when PEF (152.3-176.3 kJ/kg) was followed by HPU (3 min), inactivation levels of 8.2, 6.6 and 1.0 log-cycles were obtained for E. coli, A. niger and B. pumilus, respectively. Moreover, the inactivation achieved by the PEF-HPU treatment was higher than the sum of the individual treatments for all microorganisms. On the contrary, the inactivation achieved by HPU-PEF treatment was lower than that of the sum of the individual treatments. Thus, the most effective sequence for the combined treatment was the one in which PEF was followed by HPU. It can be concluded that, the combination of HPU with SC-CO2 or PEF generally improved the microbial inactivation. Consequently, reasonable processing times and mild process conditions could be used. / Gómez Gómez, Á. (2021). Pasteurization of Lipid Emulsions with Supercritical CO2 and High Power Ultrasound [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/175486 / Compendio

L'utilisation de membranes pour la séparation/purification de mélanges de gaz permet d'envisager la mise en œuvre de procédés continus et faiblement énergivores. Les performances des membranes étant directement reliées à la méthode utilisée pour leur synthèse/modification, une nouvelle génération de membranes est attendue à partir de la méthode originale de dépôt « dynamique » développée et mise au point dans ce travail, en milieu CO2 supercritique (CO2SC). Les propriétés des fluides supercritiques, intermédiaires entre celles d'un liquide et d'un gaz (densité et diffusivité élevées, viscosité faible), laissent en effet présager la formation de microstructures originales. Les précurseurs sont solubilisés dans le CO2 sous pression puis transportés jusqu'au support membranaire. Cette méthode a été explorée pour : i) la synthèse directe de membranes à base de silice sur des supports macroporeux et ii) la modification de membranes zéolithiques MFI par des alcoxydes (MDES, TEOS) ou par des oligomères fluorés. Dans le premier cas, l'étude des paramètres de dépôt montre que la maîtrise des phénomènes chimiques de la transition sol-gel (contrôlés principalement par la température) dicte la microstructure du matériau final, au travers du degré de condensation/réticulation des clusters déposés. La modification des membranes zéolithiques MFI par un alcoxyde permet de doubler la permsélectivité He/SF6 initiale, sans forte baisse de perméance (Π(He)~10-6 mol.Pa-1.s-1.m-2). Dans ce cas, la force, la nature et la disponibilité des sites acides de la charpente MFI sont des critères clés pour la fixation de l'alcoxyde. Les membranes MFI modifiées par un oligomère fluoré sont imperméables au SF6 et la permsélectivé He/N2 peut atteindre une valeur de 136 à 25°C (Π(He)~10-8 mol.Pa-1.s-1.m-2). Cette nouvelle méthode dynamique de dépôt/modification développée dans ce travail apparaît comme une approche très versatile qui permet de contrôler la structure du matériau déposé en ajustant les paramètres du procédé. / Using membranes for the separation/purification of gas mixtures makes possible the implementation of continuous processes with low energy consumption. Membrane performance being directly related to their synthesis/modification method, a new membrane generation is expected from the original "dynamic" deposition method which has been designed and developed in this work, in supercritical CO2 (scCO2) media. Indeed, the properties of supercritical fluids are intermediate between those of liquids and gases (high density and diffusivity, low viscosity), original membrane microstructures are expected to be derived from this process. The selected precursors are solubilized in compressed CO2 and then transported to the membrane support. This method has been explored for both: i) the synthesis of silica-based membranes on macroporous supports and ii) the modification of MFI zeolite membranes by either alkoxides (MDES, TEOS) or fluorinated oligomers. In the first case, an investigation of the deposition parameters demonstates that the sol-gel chemistry (controlled mainly by temperature) masters the final material microstructure, through the degree of condensation/crosslinking of the deposited clusters. Modification of MFI zeolite membranes with alkoxides can double their initial He/SF6 permselectivity without lowering too much their permeance (Π(He)~10-6 mol.Pa-1.s-1.m-2). In this case, the alkoxide fixation is monitored by the strength, nature and availability of acid sites in the MFI network. MFI membranes modified with fluorinated oligomers are SF6-tight and their He/N2 permselectivity can reach 136 at 25°C (Π(He)~10-8 mol.Pa-1.s-1.m-2). This new dynamic deposition/modification method developed in this work appears as a versatile approach in which the final material structure can be controlled by adjusting the process parameters.

Cette étude porte sur la décontamination de matrices textiles en milieu CO2 dense (CO2 liquide ou CO2 supercritique). Elle s'inscrit dans le cadre de la décontamination des textiles utilisés dans l'industrie nucléaire. Le CO2 dense est proposé comme alternative au milieu aqueux utilisé dans le procédé actuel et qui génère une importante quantité d'effluents aqueux contaminés nécessitant un post-traitement. Le contaminant étudié est le cobalt qui peut se présenter sous forme ionique ou particulaire. L'extraction du cobalt en milieu CO2 dense est assurée par un additif : un tensioactif macromoléculaire CO2-phile/CO2-phobe complexant. Plusieurs familles d'additifs ont été synthétisées par polymérisation radicalaire contrôlée : des copolymères à gradient comportant des motifs CO2-philes, siliciés ou fluorés, et des motifs CO2-phobes complexants de types acétoacétoxys, diéthylphosphonates ou acides phosphoniques. Le comportement de ces copolymères dans le CO2 dense a été évalué grâce à la détermination des diagrammes de phases copolymère-CO2 (par la mesure du point de trouble) et grâce à l'étude de leur autoorganisation dans le CO2 dense (par diffusion de neutrons aux petits angles). Les copolymères fluorés se sont avérés être les plus avantageux en termes de solubilité. Néanmoins, les copolymères siliciés présentent une solubilité compatible avec le procédé et ils constituent donc une alternative intéressante pour éviter la présence de fluor gênant pour le conditionnement des déchets nucléaires. L'étude de la complexation du cobalt par les copolymères (par spectrométrie UV-visible et par torche à plasma couplée à un spectromètre d'émission atomique) a permis d'établir des relations entre le type de motif complexant et l'affinité avec le cobalt. La solubilité dans le CO2 dense de ces complexes copolymères-cobalt est comparable à celle des copolymères seuls. De plus, l'étude de l'auto-organisation en milieu CO2 dense a révélé un faible taux d'agrégation des complexes copolymères-cobalt. Enfin, les copolymères synthétisés ont été mis en oeuvre dans les procédés de décontamination particulaire et ionique. Dans le cas du procédé de décontamination ionique, l'emploi du copolymère à gradient poly(acrylate de 1,1,2,2-tétrahydroperfluorodécyle-co-diacide vinylbenzylphosphonique) a permis d'atteindre environ 70% de décontamination grâce à la formation d'une microémulsion d'eau dans le CO2 dense. L'efficacité du procédé dedécontamination a été portée à 97% grâce à l'emploi de pyridine comme tiers additif. / This study is about textile decontamination in dense CO2 (liquid CO2 or supercritical CO2). The study is carried out in the framework of decontamination of textile used in the nuclear industry. The dense CO2 offers an alternative to aqueous medium used in the current process which generates a huge quantity of contaminated aqueous effluent requiring a post-treatment. Cobalt is the targeted contamination and can be found as ionic species or particles. The cobalt extraction in dense CO2 is achieved with an additive : a complexing CO2-philic/CO2-phobic macromolecular surfactant. Several types of additives were synthesized by controlled free radical polymerization : gradient copolymers made with CO2-philic groups (silicone-based or fluorinated moieties) and CO2-phobic complexing groups (acetoacetoxy, diethylphosphonate or phosphonic acid moieties). The copolymer behavior in dense CO2 was determined by phase diagram measurements (cloud point method) and their self-assembly in dense CO2 was investigated by small angle neutron scattering. The fluorinated copolymers were found advantageous in terms of solubility. Nevertheless, the silicone-based copolymers showed solubilities which are compatible with the process, therefore they are a good alternative to avoid fluorinated compounds which are unwanted in the conditioning of nuclear wastes. The study of cobalt complexation by the copolymers (UV-vis spectroscopy and inductively coupled plasma-mass spectroscopy) established relations between the type of complexing group and the affinity with the cobalt. The solubility of copolymer-cobalt complexes in dense CO2 is similar to those of copolymers. Moreover, the self-assembly study of the complex revealed a low aggregation. Finally, the synthesized copolymers were used in particle or ionic decontamination processes. In the case of ionic decontamination process, a rate of 70% of decontamination was reached with the use of gradient copolymer poly(1,1,2,2-tetrahydroperfluorodecyle acrylate-covinylbenzylphosphonic diacid) which allowed the formation of water-in-CO2 microemulsion. The efficiency of the decontamination process was even improved up to 97% with the addition of pyridine in the process.

L’extraction d’huile végétale à partir des graines repose principalement deux procédés : le pressage mécanique et ’extraction par solvants. Dans un contexte actuel de limitation de la consommation de solvants et de recherche de procédés adaptés à la production d’huile végétales thermosensibles, un procédé alternatif d’extraction d’huile a été étudié dans ce mémoire : le pressage mécanique assisté par CO2 supercritique (GAME). Pour évaluer le potentiel de cette technique en terme de rendement en huile et de co-extraction de composés antioxydants dans l’huile, l’extraction par CO2 supercritique (EPCO2-SC) et le pressage à vis (procédé de référence en trituration) ont été préalablement étudiés. Deux espèces ont été étudiées, les graines de lin et les pépins de raisin. En EPCO2-SC, des rendements en huile moins importants sont obtenus, cependant il est possible d’augmenter la teneur en polyphénols co-extraits dans l’huile par le contrôle des paramètres opératoires. L’évaluation des deux modes de pressage assisté (sous flux continu de CO2-SC et après un conditionnement en CO2-SC) a montré que le rendement en huile pouvait être augmenté de 30 à 40% en comparaison au pressage hydraulique seul malgré l’application de faibles pressions mécaniques effectives (de l’ordre de 3,5 à 7 MPa). Toutefois, les rendements obtenus restent inférieurs à ceux observés en pressage en continu. La teneur en antioxydants dans l’huile est fonction de la température et de la pression appliquée, mais reste inférieure à celle obtenue pour des conditions identiques en EPCO2-SC. / Screw pressing or solvent extraction are processes commonly used at an industrial scale to extract oil from oilseeds. However, in a context of continuous improvements, i.e. reduction ofsolvent consumption and production of high-quality oils, gas assisted mechanical expression appears as an interesting alternative, among emerging technologies. To assess the latter in terms of oil extraction yield and co-extraction of antioxidant compounds in oil, supercritical CO2 extraction and screw pressing were preliminarily studied. Two raw material were studied; flaxseeds and grape seeds. Supercritical CO2 extraction lead to low oil yields, but by controlling CO2 pressure and temperature, total polyphenol content in oil could be enhanced. For gas assisted mechanical expression, two different procedures were applied: (i) conditioning of seeds in supercritical CO2 followed by expression and (ii) expression under a simultaneous flux of CO2, flowing through the compacted seed bed. By those two procedures,oil yield could be increased from 30 to 40% by comparison to conventional hydraulic expression (even though low effective mechanical pressure were applied (3,5 to 7 MPa)). However, although antioxidant level in oil could be increased by modulating CO2 pressure and temperature for gas assisted mechanical expression, this level remained lower than those obtained in oil by supercritical CO2 extraction in the same conditions. Screw pressing enabled the highest oil yields among the three studied processes. Furthermore, oil composition was unaffected by screw pressing operational conditions.