Cette thèse présente les études de sonoluminescence multibulle (MBSL) effectuées à l’ICSM pour compléter de précédents résultats ayant mis en évidence la formation d’un plasma hors équilibre au cours de la cavitation multibulle dans l'eau. La sonoluminescence et la réactivité sonochimique de l’eau sous flux continu de mélanges gaz rare et N2 et d’une solution aqueuse d’ammoniaque sous flux continu de gaz rare sont étudiées par plusieurs techniques expérimentales. Nous avons observé, en plus de l’émission de OH (A2Σ+-X2Πi) et du continuum typique de SL, pour la première fois la sonoluminescence de NH (A3Π – X3Σ-). Les spectres de sonoluminescence, le suivi des rendements de formation des produits de la sonolyse et les résultats de fits de NH (A3Π- X3Σ-) et OH (A2Σ+-X2Πi) en utilisant le logiciel Specair confirment l’atteinte de conditions plus extrêmes au moment de l’implosion des bulles à haute fréquence ultrasonore. D’autre part, ces résultats indiquent clairement l’absence d’équilibre thermique à l’intérieur des bulles de cavitation au moment de l’implosion (Tv > Tr) quelles que soient les conditions expérimentales, et que la température vibrationnelle est plus élevée à haute fréquence US ce qui conduit au non suivi de la loi de Boltzmann des populations des niveaux vibrationnels et/ou rotationnels. En parallèle, l’évolution de la taille des bulles de cavitation a été mesurée par une technique d’ultrasons pulsés, dans le cadre d’une collaboration entre l’ICSM/LSFC et l’université de Melbourne en Australie. Nous avons en particulier mis en évidence un problème de coalescence des bulles sous flux continu de gaz, qui complique grandement l’interprétation des résultats de taille des bulles. Une autre observation est que la présence d’azote dans l’argon conduit à une diminution de la taille des bulles. / This thesis presents the studies on multibubble sonoluminescence (MBSL) performed at ICSM to complete previous results that have shown the formation of a non-equilibrium plasma in the multibubble cavitation in water. Sonoluminescence and sonochemical reactivity of water under continuous flow of noble gas and N2 mixtures and of aqueous ammonia solutions under continuous flow of noble gas are studied by several experimental techniques. In addition to OH (A2Σ+-X2Πi) band and continuum emission usually observed in the SL spectra of water in the presence of noble gases, the sonoluminescence of NH (A3Π) radicals was observed for the first time. Spectroscopy of sonoluminescence, the follow up of the sonochemical products and the spectral fits of NH (A3Π- X3Σ-) and OH (A2Σ+-X2Πi) systems using Specair software indicate more drastic conditions at high US frequency. On the other hand, NH* and OH* radicals generated inside the cavitation bubbles are far from equilibrium (Tv > Tr) whatever the experimental conditions and the vibrational temperatures at high frequency ultrasound are much higher compared to 20 kHz ultrasound which leads to strong deviation from the equilibrium (non-Boltzmann behavior). In parallel, the evolution of the bubble size is measured by a pulsed ultrasound technique, in the framework of a collaboration between ICSM / LSFC and the University of Melbourne in Australia. The problem of the coalescence of bubbles under continuous flow of gas was identified, which greatly complicates the interpretation of results of bubble size. Another interesting observation is that the presence of nitrogen in argon leads to a strong reduction in bubble size.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2017. / Coal fly ash waste produced from the coal combustion process is becoming an ever increasing concern. It is produced in such abundance due to not only South Africa, but the whole of the world relying mainly on coal combustion for the main source of energy production. With the growing rate of the human population this energy production is ever increasing. The current methods of disposal of this fly ash is not sustainable, it is being dumped in ash dumps, and poses a risk to the surrounding environment and human population. Therefore, processes need to be developed to take this waste and turn it into useful materials. This would not only solve the problem of its disposal but also create useful products that can be applied to further protect the environment. It was discovered that one of the useful materials that can be synthesised from fly ash are zeolites. These nano-porous structures have a wide variety of uses. Therefore, many studies have been conducted around optimising the synthesis of various zeolites from coal fly ash. More recently these studies have focused on the scale-up conditions needed to synthesise these zeolites on the large industrial scale, regarding the sheer volume of fly ash produced annually. The most robust and widely used technique for zeolite synthesis involves a pre-synthesis fusion of the fly ash with sodium hydroxide at a temperature of 550 0C. This would not be feasible to scale-up to industrial scale because of the energy intensity. Therefore, alternative pre-synthesis techniques have been proposed. One of those techniques involves using a sonochemical treatment as a pre-synthesis. It can be argued that this technique may not be able to be easily scaled. To solve this problem, another alternative technique was investigated within this study. It involves the use of a jet loop pilot plant mixing system, which can be scaled-up very readily to industrial scale.

Les métamatériaux sont des matériaux artificiels, formés par l’assemblage de nano-résonateurs, qui ont la capacité d’interagir avec les ondes qui les traversent et de conférer des propriétés inaccessibles aux matériaux homogènes. Afin de fabriquer de tels métamatériaux agissant dans le domaine du visible, un contrôle précis de l’organisation des résonateurs à l’échelle nanométrique est requis. Dans ce projet nous avons donc élaboré des voies de fabrication de type bottom-up, en organisant de façon anisotrope des nanoparticules d’or (AuNPs), qui sont des résonateurs du fait de leurs propriétés plasmoniques, dans un film de copolymères à blocs poly(styrène)-b-poly(vinylpyridine) (PS-b-PVP) nano-structuré en rangées de cylindres de PVP perpendiculaires au substrat.Au cours de ce projet, nous avons élaboré des routes de formulation permettant de produire des films de phase cylindrique hexagonale de copolymères alignés contenant des nanoparticules d’or. L’orientation des cylindres perpendiculaires au substrat a été obtenue en déposant le copolymère grâce à un solvant neutre dont la composition dépend de la fraction volumique en PVP du copolymère. La structure des films avec et sans nanoparticules a été caractérisée par microscopie et diffusion des rayons X en incidence rasante (GISAXS). Plusieurs méthodes d’incorporation des nanoparticules d’or ont été étudiées, soit en synthétisant les nanoparticules au sein du copolymère, en solution avant dépôt ou directement dans le film organisé ; soit en incorporant des nanoparticules pré-formées, en solution de copolymère ou dans le film déposé. Dans le cas de la synthèse in situ, nous avons formé les AuNPs par réduction chimique ou physique (sonication, radiolyse) d’un sel d’or dans le copolymère. L’incorporation des AuNPs pré-formées, elle, a été réalisée grâce à la fonctionnalisation des AuNPs ou par un traitement du film de copolymère afin de faciliter l’insertion des AuNPs. / Metamaterials are artificial materials, made from the assembly of nano-resonators, which can interact with incoming waves and get properties unknown for homogeneous materials. In order to fabricate metamaterials with an effect over visible light, a precise control over the organization at the nanoscale is required. The goal of this project was then the use of bottom-up approaches to achieve the anisotropic organization of gold nanoparticles (AuNPs), which are resonators due to their plasmonic properties, into a poly(styrene)-b-poly(vinylpyridine) block copolymer film, with a nanostructuration in arrays of PVP cylindrical domains perpendicular to the substrate.During this work, we investigated routes for the fabrication of copolymer films containing ordered gold nanoparticles in a hexagonal cylindrical phase. The orientation of the cylinders normal to the substrate was obtained by casting the copolymer with a neutral solvent whose composition was found dependent on the volumic fraction of PVP in the copolymer. The film structure with and without AuNPs was characterized by microscopy and Grazing-Incidence Small-Angle X-rays Scattering (GISAXS). Several incorporation methods for the insertion of AuNPs were studied, either by the in situ synthesis of the nanoparticles in solution before casting or directly into the ordered film; or by incorporating pre-formed AuNPs in the copolymer solution or in the film as-cast. In the case of the in situ synthesis, the AuNPs were formed by chemical or physical (sonication, radiolysis) reduction of a gold salt in the copolymer. The incorporation of pre-formed AuNPs was, achieved thanks to the functionalization of the AuNPs or by a treatment of the copolymer film in order to facilitate the insertion of the AuNPs.

Os meios confinados restringirem o grau de liberdade dos reagentes e podem afetar significativamente seus estados energéticos e perfis de coordenada de reação. Macrociclos são muito utilizados nessa perspectiva graças a capacidade de hospedar moléculas em suas cavidades e modificar o momento de dipolo das mesmas. Isso permite que estes cavitandos sejam usados como catalisadores, sensores ou simples carreadores, por exemplo. A bambus[6]urila (BU[6]), sintetizada recentemente, ganhou atenção graças à sua capacidade de formar caviplexos estáveis com ânions. Os reagentes de partida são glioxal e ureia, compostos relativamente baratos e comuns, mas a rota síntetica descrita na literatura, no entanto, não contém uma série de informações importantes, o que dificulta a síntese da BU[6]. Muitos estudos computacionais foram realizados para prever e entender as interações deste macrociclo com outras moléculas. No entanto, informações relevantes sobre a BU[6] como a estabilidade térmica, capacidade de complexar cátions ou solubilidade em soluções salinas e solventes comuns, ainda não foram publicados. Nesse trabalho foram determinadas as propriedades fundamentais (densidade, condutividade elétrica e pH de solução saturada, ponto de fusão) da BU[6] vazia e de seu caviplexo BU[6]HCl, bem como a estabilidade térmica das mesmas por meio de análises termogravimétricas. Além disso, tentamos reduzir o tempo de síntese BU[6]HCl utilizando ultrassom e os produtos obtidos foram analisados por técnicas espectrométricas e espectroscópicas. A solubilidade da BU[6]HCl foi estudada utilizando diversos solventes, soluções salinas de metais alcalinos e alcalino-terrosos e meios com diferente acidez. Titulações condutimétricas de soluções de BU[6]HCl com soluções salinas de metais alcalinos e alcalino-terrosos foram realizadas para avaliar a interação entre a BU[6] e os cátions. Por fim, foram realizados experimentos para avaliar a interação dos gases bromo e iodo com as BU[6] vazia e BU[6]HCl, em estado sólido, e os produtos obtidos submetidos à analises espectroscópicas e espectrométricas. / Confined media restrain degrees of freedom and can affect considerably their energetic states and reaction coordinate profiles. Macrocycles are widely used for such purpose thanks to their capacity to include molecules in their cavities, changing their eletric dipole moments. This is why they can be used as calalyst, sensors or simple carriers for example. Bambus[6]uril (BU[6]), recently synthesized, has drawn attention due to its ability to form stable caviplexs with anions. The starting reagents are glyoxal and urea, two afordable and common compounds, but the synthetic route described in the literature however, lacks many important information make it difficult to prepare BU[6]. Many computer calculations were done to preview and understand the interactions between this macrocycle and other molecules. However, relevantly informations about BU[6], such as thermal stability, its ability to complex cations or its solubility in salt solutions and common solvents were not published yet. In this work the fundamental properties (density, pH and conduvity of saturated solution, melting point) of empty BU[6] and BU[6]HCl has been determined, as well the thermal behaviour of the compounds by thermogravimetric analysis. Beyond that, we have attempted to reduce BU[6]HCl synthesis time using ultrasound and the obtained products were analyzed by spectrometric and spectroscopic techniques. The solubility of BU[6]HCl has been studied with diversal solvents, alkaline and alkaline earth metals saline solutions and different acidity media. Condutimetric titrations of BU[6]HCl with alkaline and alkaline earth metals saline solutions were realized to evaluate the interaction of BU[6] and cations. Lastly, experiments to evaluate the interaction between the gases bromine and iodine with empty BU[6] and BU[6]HCl, in solid state, were realized and the obtained products submitted to spectroscopic and spectrometric analysis.

Catalysis is one of the Green Chemistry Principles given its importance for limiting environmental impacts and improving current processes, as well as for developing new sustainable processes and products. In order to provide more performant catalysts, this study provides a novel preparation method for controlling the distribution of metal nanoparticles (NPs) within hierarchically meso- and macroporous catalysts. It consists of the combination of latex synthesis, sonochemistry and sol-gel process. All these steps can be carried out in water, reducing environmental impact. The first step is the synthesis of latex, typically polystyrene. The second step is the sonochemical synthesis and deposition of noble metal NPs on the surface of the latex polymer. The third step is the synthesis of the support by sol-gel process using tetraethyl orthosilicate (TEOS) under controlled conditions to modulate the porosity of the final silica matrix. As a result, an original catalyst morphology is obtained with active sites preferentially located within the macropores, which are surrounded by a mesoporous matrix. Using this approach, a monodisperse polystyrene latex (~130 nm) was prepared by emulsion polymerisation and then decorated with Pt NPs (~2.3 nm) by sonochemical reduction. The mesoporous silica support was prepared by sol-gel synthesis in the presence of the decorated latex. After calcination, the organic template left behind macropores with the Pt NPs within the generated macropores. Mesopores (2-15 nm) connecting these macropores (110-400 nm) were tuned by varying the synthesis conditions. Typically, specific surface areas of 615 m2/g and total pore volumes of 0.74 cm3/g were obtained. In a first case of study, hierarchically porous Pt/SiO2 catalysts were evaluated in the selective hydrogenation of p-chloronitrobenzene (p-CNB) to produce p-chloroaniline. They exhibited activities up to 91.7 ± 2.9 molCNB/(min molPt) and selectivity values up to 100 ± 2% at 80% of conversion, in comparison with 47.7 ± 2.9 molCNB/(min molPt) and 91 ± 2%, respectively, obtained with a commercial catalyst under the same conditions. Moreover, in a second case of study, it was possible to prepare silica-supported Pd, Pd-Pt and Pd-CeO2 catalysts with hierarchical porosity (meso and macro). These materials were tested in the direct synthesis of hydrogen peroxide from hydrogen and oxygen. The best productivity of H2O2 was obtained with the bimetallic Pd-Pt catalyst with 32500 molH2O2/(h molmetal) in batch, and the best selectivity was obtained with Pd-CeO2/SiO2 catalyst (63 ± 2%) in semi-batch. In summary, this thesis proposes a new aqueous preparation method for hierarchically porous functional materials by the combination of latex synthesis, sonochemical reduction and sol-gel process. It has been demonstrated that this preparation technique provides a very powerful and versatile toolbox for catalyst tailoring and optimisation. Further perspectives to achieve improved morphologies and controlled active sites distribution are also proposed. / La catalyse est l'un des piliers pour le développement de procédés durables, car elle permet d'utiliser moins de ressources en accélérant les réactions chimiques. Afin de fournir des catalyseurs plus performants, cette étude propose une nouvelle méthode de préparation de catalyseurs pour contrôler la distribution de nanoparticules (NPs) métalliques au sein des catalyseurs hiérarchiquement poreux (méso et macro) en combinant la synthèse de latex, la réduction sonochimique et le procédé sol-gel. La première étape est la synthèse d'une empreinte porogène de billes de polystyrène (latex) obtenues par polymérisation en émulsion aqueuse. La deuxième étape est la synthèse et le dépôt de NPs de métaux nobles sur la surface des billes de polymère par voie sonochimique dans l’eau. La troisième étape est la synthèse du support catalytique par un procédé sol-gel en milieu aqueux en utilisant le latex décoré et l’orthosilicate de tétraéthyle (TEOS) dans des conditions contrôlées pour moduler la porosité finale de la matrice de silice (mésoporeuse). Toutes les étapes de cette approche sont effectuées dans l'eau, ce qui limite les impacts environnementaux de la préparation du catalyseur. L'élimination du porogène (latex) par calcination génère les macropores. Le matériau résultant possède alors une morphologie inédite pour un catalyseur, avec des macropores fonctionnalisés par des NPs métalliques, dans une matrice de silice mésoporeuse. Ainsi, il a été possible de synthétiser un latex monodisperse de polystyrène (~130 nm), lequel a été décoré avec des NPs de Pt (~2.3 nm) par réduction sonochimique. Le matériau final de silice a présenté des mésopores (2-15 nm) reliant les macropores (110-400 nm) contenant les NPs de Pt. Il a été possible d'obtenir des surfaces spécifiques et des volumes poreux totaux de 615 m2/g et 0,74 cm3/g, respectivement. Dans un premier cas d'étude, des catalyseurs de Pt/SiO2 à porosité hiérarchique ont été évalués dans l'hydrogénation sélective du p-chloronitrobenzene (p-CNB) pour produire la p-chloroaniline. Ils ont présenté des activités catalytiques allant jusqu'à 91,7 ± 2,9 molCNB/(min molPt) et des sélectivités jusqu'à 100 ± 2% à 80% de conversion, par rapport à 47,7 ± 2,9 molCNB/(min molPt) et 91 ± 2%, respectivement, obtenus dans les mêmes conditions avec un catalyseur commercial. Dans un deuxième cas d'étude, des catalyseurs à base de Pd, Pd-Pt et Pd-CeO2 supportés sur de la silice à porosité hiérarchique ont été préparés et testés dans la synthèse directe du peroxyde d'hydrogène. La meilleure productivité a été obtenue avec le catalyseur bimétallique Pd-Pt avec 32500 molH2O2/(h molmétal) en batch, et la meilleure sélectivité a été obtenue avec le catalyseur Pd-CeO2/SiO2 (63 ± 2%) en semi-continu. En résumé, cette thèse propose une nouvelle méthode de préparation dans l’eau de matériaux fonctionnels à porosité hiérarchique en combinant la synthèse de latex, la réduction sonochimique et le procédé sol-gel. Il a été démontré que cette technique de préparation fournit une boîte à outils très puissante et polyvalente pour la préparation et l'optimisation des catalyseurs. Des perspectives pour améliorer davantage les morphologies et la distribution contrôlée des sites actifs sont également proposées.

Process industries are cornerstones in today’s industrialized society. They contribute significantly in the manufacturing of various goods and products that are used in our day-to-day life. Our society’s paradigm of consumerism accompanied by a rise in global population drives an ever increasing demand for goods. One of many strategies developed to satisfy these demands and at the same time improve production capabilities is known as process intensification. As an example, this can be accomplished by implementation of devices using the principle of hydrodynamic and acoustic cavitation. High-intensity cavitation in the ultrasonic range can change the physical and chemical properties of a wide range of substances and hence, improve the production rate or quality. Despite the generally accepted benefits of hydrodynamic and acoustic cavitation, applications in the process industry are yet limited. The reasons are that the method requires extensive optimization, which depends on multiple process parameters and encounters problem in the implementation on a larger scale. Scalable cavitation reactor concepts for industrial applications need to meet challenges like stability and robustness, energy efficiency and high flow rates. This thesis focuses on the methodology for the design and optimization of a flow through cavitation reactor. An ultrasound reactor concept has been developed and tested for two different applications: i) Fibrillation processes typical for paper and pulp industry; ii) Metal leaching of mineral concentrates. Simulations were carried out using a commercially available software for multiphysics modeling which combines acoustics, structural dynamics, fluid dynamics and piezoelectrics. However, the optimization procedure requires extensive experimental work in parallel with multi-physical simulations. In general, the application leads to hydrodynamic initiation of small gas bubbles in the fluid to be excited and collapsed by high-intensity ultrasound. This transient collapse of the cavitation bubbles provides both mechanical and chemical effect on materials. The developed reactor has a power conversion efficiency of 36% in batch mode and is well suited for a scale-up. In flow-through mode, the cavitation effect improves extensively and provides stable results. Energy efficiency requires hydrodynamic initiation of cavitation bubbles, high acoustic cavitation intensity by multiple excitation frequencies adapted to the optimized reactor geometry, as well as optimal process pressure and temperature with respect to the materials to be treated. The impact of flow conditions and hydrodynamic cavitation is significant and almost doubles the yield at the same ultrasonic power input. In the case of fibrillation of cellulose fibers, results obtained indicate that generated cavitation intensity changes the mechanical properties of the fiber wall. In the case of leaching, experiments show that six hours of exposure gave a 57% recovery of tungsten from the scheelite concentrate at 80°C and atmospheric pressure. Future research will focus on different types of excitation signals, extended reactor volume, increased flow rates and use of a higher process temperature.

No description available.

No description available.

Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: It was found that bacterial sludge from anaerobic water treatment systems is produced internationally at a rate of 60 grams per person per day and the accumulation of the potentially hazardous by-product has become of increasing concern. The produced bacterial sludge is frequently pumped into dams, dried out and used as agricultural fertilizer. This bacterial sludge is expected to have a relatively high heating value and as such, has the potential to produce energy from the biomass. It is, therefore, advisable to utilize this energy potential as an alternative to conventional sludge disposal. This project aimed to improve the yield of syngas by optimizing the reactor design to partially oxidize bacterial sludge using a sonochemical reactor that is operated at bulk atmospheric conditions. The effect of different conditions was investigated and the optimum settings for syngas production were found by investigating temperature, pressure and the effect of the amplitude of operation that regulates the energy input by the ultrasonic equipment. The optimum conditions were used to investigate the kinetics involved in this process as well as to determine the energy consumption by the process. It was also required to study the feasibility of partially oxidizing bacterial sludge using a sonochemical reactor instead of conventional steam gasification and also as an alternative means of sludge disposal. By eliminating this pollutant source, the future environmental threat posed by an increasing population size will be minimized and energy will be utilized from a thus-far wasted energy source. The syngas that is produced is used as a green alternative to fossil fuels in the Gas-to-Liquids (GTL) process to produce liquids fuels. A thus-far wasted energy source will be consumed and fossil fuels can be saved in the process. It was found that the maximum hydrogen mole percentage produced is 0.141 mole % of the vapour phase with the maximum carbon monoxide mole percentage in the vapour phase at 1.896 mole %. This shows an improvement on work conducted by Beyers (2011) of 59 % for hydrogen, 92% for carbon monoxide and a reduction of 49 % for carbon dioxide. A kinetic study of the process indicated that the rate equations that describe the hydrogen and carbon monoxide production are zero order and, therefore, independent of initial concentration of the sludge. The rate constants were 0.0146 (mol % hydrogen/s) and 0.0183 (mol % hydrogen/s) for hydrogen and carbon monoxide, respectively. It was found that the most severe change to the higher heating value of the feed was a mere 0.27 mJ/kg from an original value of 9.81 mJ/kg. This therefore confirms that the reaction has not proceeded to completion. The statistical model predicted a maximum value for hydrogen production at 0.151 mole % in the product gas, 0.01 mole % from the measured maximum. It was also found that hydrogen is produced during the sonolysis of distilled water and that this confirms that the hydrogen production during partial oxidation of the sludge sample comes mainly from the water present in the sludge. The hydrogen produced when only using water, was found to be 0.127 mole % and when using the active sludge, the value was 0.116 mole % hydrogen in the vapour phase. The thermal decomposition of calcium carbonate in the lime that is used to treat the pH of the unit where the sludge originates from, followed by the formation of carbon monoxide during the Boudouard reaction, led to an increased amount of carbon monoxide present in the product gas. Ultrasonic intensity is defined as the amount of energy that is transferred to the sample per cubic meter of the internal surface area of the reactor vessel. It was found that the intensity that was delivered to the reactant was lower than expected as the reactor was operating at an efficiency of only 36%. The design intensity was 1.44 W/m2 and the actual delivered intensity was 0.52 W/m2. Based on a maximum yield of 0.00012 Nm3/kg, the cost of syngas production under the conditions described by this study, would amount to R 19.98/Nm3. This cost only implicates the operational expenses and does not take further downstream processing and initial capital investment repayments into account. Conventional steam gasification at a yield of 0.67 Nm3/kg has an operational syngas production cost of R 1.48/Nm3. This process was therefore found to not be economically feasible as the cost of utilizing ultrasound as opposed to normal steam gasification is more than ten times more expensive. It was concluded that the process was successfully optimized by the redesigning of the reactor and that carbon dioxide production was limited by excluding oxygen from the feed gas. It was also concluded that the sonolysis of water and the thermal decomposition of calcium carbonate, followed by the conversion of carbon dioxide to carbon monoxide, supplements the syngas production under the current operational conditions. Based on the production of no methane during the course of this study, the sonochemical process can be tied into the GTL process after the steam reforming unit. Due to the relatively high carbon dioxide content, the process will need to join the main feed gas stream that is fed into the carbon dioxide removal unit before it enters the GTL process to correct the desired feed gas ratio. Based on the very low syngas yields, the low hydrogen to carbon monoxide ratio in comparison to the required ratio of 2 as well as the high energy intensity required for this process, it can be concluded that the partial oxidation of biomass sludge in a sonochemical reactor is not feasible as an alternative technology to conventional steam gasification. The operating costs of the sonochemical unit would be nearly ten times that of steam gasification and is therefore concluded to not be a competitive technology to conventional steam gasification. It is recommended that the reactor design is reinvestigated to improve the delivered ultrasound intensity as well as the surface area where the ultrasonic waves are intensified. This would eliminate dead-zones. It was also recommended that the argon gas is continuously bubbled through the reactant mixture during experiments to eliminate the degassing effect caused when the ultrasound is initially emitted. The gas outlet of the process can then be connected to an online gas chromatograph (GC) with a thermal conductivity detector (TCD) and flame ionization detector (FID) methanizer in series as the TCD does not destroy the sample and this setup would improve the analytical process. The production of carbon monoxide from lime as well as the production of hydrogen from water during sonolysis needs to be investigated. The effect of radicals can also be studied by the addition of a radical scavenger to the process. It is recommended that the experimental design is reinvestigated and a design that will deliver similar information utilizing fewer data points should be chosen. Based on this model as well as further kinetic testing, it is recommended that a complete ASPEN model is developed to simulate the energy requirements to tie the ultrasonic process into the commercial plant. Based on this model, a complete feasibility study can then be conducted to determine the capital costs involved, the operating costs, the repayment period as well as taking the current costs of sludge disposal into account. / AFRIKAANSE OPSOMMING: Daar is gevind dat bakteriele slik internasionaal geproduseer word deur anaerobiese waterbehandelingseenhede teen ‘n tempo van 60 gram per person per dag en dat die opberging van hierdie gevaarlike byproduk ‘n groeiende probleem word. Die geproduseerde bakteriele slik word in damme gestoor, uitgedroog of gebruik as kunsmis in die landbou bedryf. Daar word vermoed dat hierdie baketriele slik oor ‘n hoe verwarmings waarde beskik en het daarom die potensiaal om energie te produseer uit die biomassa. Daarom is dit voorgestel om alternatiewe prosesse te ondersoek om van hierdie slik ontslae te raak en moontlik die energie wat beskikbaar is te gebruik. Die projek is daarop gefokus om die produksie van syngas te verbeter deur die reaktorontwerp te optimeer deur gebruik te maak van parsiele oksidasie van slik onder atmosferiese kondisies deur klankgolwe te gebruik. Die effek van verskillende operasionele kondisies is ondersoek en die optimale vlakke van syngas produksie is gevind deur temperatuur, druk en amplitude wat die hoeveelheid energie wat oorgedra word aan die reaktor reguleer, te ondersoek. Die optimale kondisies is ook gebruik om die kinetiese aspekte van die proses te ondersoek en ook om te kyk wat die sisteem se energie benodighede behels. Die haalbaarheid om baketriele slik parsieel te oksideer in ‘n sonochemiese reaktor is vergelyk met dit van konvensionele stoom vergassing van die biomassa en is ook ondersoek as ‘n alternatief om van die slik ontslae te raak. Deur die slik te verwyder as ‘n potensiele bron van besoedeling, kan die toekomstige omgewing’s risiko wat deur die toename in die bevolkkingsgroote tot gevolg is, verwyder word deur ‘n energie bron te gebruik wat tot dusver geignoreer is. Die syngas wat geproduseer word kan dan gebruik word in die “Gas-to-Liquids” (GTL) process om vloeistof brandstowwe te produseer. Dus sal ‘n omgewingsrisiko verminder word, ‘n energiebron word benuttig wat nooit van tevore benuttig is nie en fosiel brandstowwe kan gespaar word. Die maksimum waterstof wat geproduseer is, was 0.141 mol % in die gas fase met ‘n maksimum waarde vir koosltof monoksied van 1.896 mol % in die gas fase. Dit toon ‘n verbetering van 59 % vir waterstof, 92 % vir koolstof monoksied en ‘n vermindering van 49% in die koolstof dioksied wat deur Beyers (2011) geproduseer is. Die kinetiese studie het ondervind dat die “rate equation” van waterstof en koolstofmonoksied beskryf word deur nul-orde kinetika. Hierdie konstantes was 0.0146 (mol % waterstof/s) en 0.0183 (mol % waterstof/s) vir waterstof en koolstofmonoksied. Daar is ook gevind dat die grootste moontlik verandering in die hoe verwarmings waarde van die biomassa is ‘n skamele 0.27 mJ/kg van die oorspronklike waarde van 9.81 mJ/kg. Hierdie waarneming staaf dus die uitkoms dat die reaksie dus nie tot die einde verloop het nie. Die statistiese model het ‘n maksimum van 0.151 mol % voorspel wat 0.01 mol % meer was as die waarde wat gemeet is. Dit is ook gevind dat waterstof geproduseer word deur die sonoliese van water en dat hierdie bykomende waterstof deel uitmaak van die produkgas aangesien die slik grootliks uit water bestaan.Die hoveelheid waterstof in die gas fase wat geproduseer is tydens sonoliese van ‘n suiwer water monster, was 0.127 mol %. Die hoeveelheid waterstof in die gas fase wanneer die slik behandel is ten optimal kondisies, was 0.116 mol % gemiddeld. Die hitte degradering van kalsium karbonaat wat teenwoordig is in die kalk wat gebruik word om die pH van die produksie eenheid te reguleer, gevolg deur die Boudouard reaksie, het tot gevolg dat addisionele koolstof monoksied ook gevorm word. Ultrasoniese intensiteit kan gedefineer word as die hoeveelheid energy wat oorgedra word aan ‘n reaktant gebasseer op die oppervlak area aan die binnekant van die reaktor. Die intensiteit waarteen die voermateriaal blootgestel word aan die klankgolwe was laer as verwag met ‘n 36 % effektiwiteit. Die ontwerp spesifiseer ‘n intensiteit van 1.44 W/m2 en die intensiteit wat fisies gelewer is, was 0.521 W/m2. Die maksimum produksie van syngas was 0.00012 Nm3/kg, wat lei tot ‘n operasionele koste van R 19.98/Nm3 onder die kondisies van hierdie studie. Hierdie koste neem nie die oorsponkilke kapitaal vir die konstruksie, of die koste van verdere behandelik van die gas, in ag nie. Konvensionele stoom vergassing teen ‘n opbrengs van 0.67 Nm3/kg het ‘n operasionele koste van R 1.48/Nm3 tot gevolg. Die proses is dus ekonomies nie ‘n aantreklike opsie nie aangesien die kostes van syngas produksie met ultraklank meer as tien keer meer is as konvensionele stoom vergassing. Daar is tot die gevolgtrekking gekom dat die reaktor optimering suksesvol was en deur geen stuurstof te voer nie, die koolstofdioksied persentasie verminder is. Daar is ook tot die gevolgtrekking gekom dat die sonoliese van water, en die hitte degradering van kalsium karbonaat, gevolg deur die Boudouard reaksie, die syngas produksie supplementeer. Aangesien geen metaan gedurende hierdie studie geproduseer is nie, kan die sonochemiese proses inskakel by die GTL aanleg na die stoom hervormingseenhed. As gevolg van die hoe koolstofdioksied konsentrasie, sal die prosesstroom gemeng moet word met die produk stroom uit die stoom hervormings proses, wat gevoer word na die koolstofdioksied verwyderings eenheid. Hierdie eenheid is daarvoor verantwoordelik om die korrekte verhouding van gasse vir die GTL voer stroom te reguleer. Gebasseer op die baie lae syngas opbrengs, die lae waterstof tot koolstofmonoksied verhouding en die hoe energie behoeftes, is daar tot die gevolgtrekking gekom dat die parsiele oksidasdie van die biomassa in ‘n sonochemiese reaktor nie ‘n haalbare alternatief is vir konvensionele stoom vergassing nie. Die operasionele koste van die sonochemiese eenheid is ongeveer tien keer meer as die van stoom vergassing en daarom is die proses nie kompeterend nie. Daar word voorgestel dat die reaktor ontwerp hersien word om die gelewerde intensiteit te verbeter, sowel as om die kontak area waar die klankgolwe gekonsentreer is, te vergroot. Dit sal dooie sones uitskakel. Daar word ook voorgestel dat argon gas gedurende die eksperiment aanhoudende geborrel word deur die reaktant vloeistof in die reaktor om die ontgassingseffek uit te skakel sodra die klankgolwe aangeskakel word. Die gas uitlaat kan dan inlyn gekoppel word aan ‘n gas chromatograaf met ‘n termiese geleidings detektor (TCD) en ‘n vlam ionisasie detektor (FID) met metaan omskakeling, aangesien die TCD nie die monster vernietig nie. Hierdie opstelling behoort analitiese methodes te verbeter. Die produksie van koolstofmonoksied uit kalk sowel as die produksie van waterstof uit water gedurende sonoliese, moet verder ondersoek word. Die effek van radikale kan ook verder bestudeer word deur die gebruik van ‘n radikaal rower gedurende die proses. Daar word ook voorgestel dat die statistiese ontwerp herondersoek word sodat minder eksperimente gebruik kan word om soortgelyke resultate te bekom met minder data punte. Gebasseer op hierdie nuwe model en ‘n kinetiese studie, word dit aangeraai dat ‘n volledige ASPEN model gebou word om te simuleer hoe hierdie sonochemiese eenheid sal inskakel met die kommersiele eenheid. Dit sal dan moontlik wees om die energie benodighede van die proses te verstaan en gebasseer daarop, kan ‘n volledige haalbaarheid studie gedoen word wat kyk na oorspronklike installasie kostes, onderhouskostes, operasionele kostes sowel as die terugbetaling van die konstruksie kostes. Dan kan ‘n vergelyking getref word met die huidige kostes om van hierdie slik ontslae te raak en om die slik as ‘n brandstof te benut.

Les oxydes mixtes de cérium-zirconium sont au cœur de nombreux sujets de recherche. En effet, ces matériaux sont utilisés dans différents domaines d'application, et tout particulièrement en catalyse, dans les catalyseurs trois voies en automobile ou pour l'oxydation de polluants organiques. L'intérêt pour ce composé réside dans ses propriétés remarquables d'oxydoréduction, sa capacité de stockage de l'oxygène et sa résistance au frittage. En conséquence, un nombre important de méthodes de synthèse ont été mises au point et soulignent la grande sensibilité de cet oxyde mixte à la voie de préparation employée. Dans le cadre de ce travail deux grandes voies de synthèses ont été utilisées, la co-précipitation (milieu aqueux) et la dégradation des -dicétonates métalliques (milieu non aqueux). Ces synthèses ont été réalisées à l'aide de plusieurs techniques que sont (i) le chauffage à pression atmosphérique, (ii) le traitement hydrothermal, (iii) la sonolyse et (iv) la combinaison de la sonolyse et du traitement hydrothermal, de façon successive ou en simultané. Afin de pouvoir réaliser cette dernière méthode de synthèse innovante, un réacteur permettant de réaliser un traitement sonochimique en température et sous pression a été développé (réacteur sonothermal). L'activité chimique des ultrasons dans ces conditions a pu être mise en évidence lors de la sonolyse de l'eau (légère ou lourde) et de celle d'un hydrocarbure. Au cours de la préparation de (Ce,Zr)O2, des paramètres autres que le dispositif de synthèse ont été étudiés, comme la présence d'un surfactant ou la longueur de chaine du solvant. Ainsi, il a pu être démontré que, dans le cas de la voie aqueuse, l'utilisation du réacteur sonothermal a une réelle incidence sur la surface spécifique du matériau final en comparaison de la réalisation successive des traitements sonochimique et hydrothermal. Les oxydes présentant les propriétés structurales les plus intéressantes ont été sélectionnés afin d'être employé en tant que support de métal noble dans des catalyseurs de type Pt/(Ce,Zr)O2. L'évaluation de l'activité catalytique de ces matériaux, lors de l'oxydation catalytique à l'air humide de l'acide formique, a montré que celle-ci dépend non seulement du mode de synthèse de l'oxyde mixte, mais également de la voie de dépôt du platine et du couple méthode de dépôt du platine/méthode de synthèse du support. / Cerium-zirconium mixed oxides are at the heart of numerous research subjects. Indeed, these materials are used in different fields of application, and particularly in catalysis in three-way catalyst for automobile or for organic pollutant oxidation. The interest for this compound resides in its remarkable oxidoreduction properties, its oxygen storage capacity and its resistance to sintering. Consequently, numerous preparation methods have been developed and underline the high sensitivity of these oxides to the synthesis way. In the present work, two main synthesis have been employed, coprecipitation (aqueous medium) and  diketonate degradation (non-aqueous medium). These syntheses have been realized with several techniques which are (i) heating at atmospheric pressure, (ii) hydrothermal treatment, (iii) sonolysis and (iv) combination of sonolysis and hydrothermal treatments, in a successive or simultaneous way. In order to realize this last and innovative method, a reactor allowing sonochemical treatment under high temperature and pressure has been developed. Under these conditions, the ultrasounds chemical activity has been proved during light or heavy water or hydrocarbon sonolysis. During the (Ce,Zr)O2 preparation, other parameters than the synthesis technique have been studied such as the surfactant presence or the solvent chain length. Thus, it has been shown that, in the case of aqueous synthesis, the use of the sonothermal reactor has a real effect on the specific surface area of the material in comparison of successive realization of sonochemical and hydrothermal treatments. Oxides with the more interesting structural properties have been selected for being used as supports of noble metal in the Pt/(Ce,Zr)O2 catalysts. The evaluation of the catalytic activity of these materials, during the catalytic wet air oxidation of formic acid, showed that it not only depends on the synthesis method, but also on the platinum deposition method and the pair platinum deposition method/support synthesis method.