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La compréhension de la structure des verres est actuellement à l’origine de nombreuses recherches scientifiques. L’une des preuves expérimentale d’un certain ordre dans ceux-ci est la séparation de phase. En effet, ce phénomène est lié à la présence dans ces matériaux amorphes d’au moins deux phases de composition chimique différentes. Ainsi, une étude des prémices de la séparation de phase de type nucléation-croissance dans des verres de silicate de sodium a été menée. La RMN c’est révélée la plus efficace pour cette étude. L’utilisation des expériences de corrélation 29Si-29Si a permis de sonder le réseau silicaté à des échelles plus grandes que celles communément considérées. Nous avons donc pu identifier ce phénomène, caractériser la composition des phases qui apparaissaient et enfin établi un lien avec la cristallisation observée pour de long temps de recuits. A l’inverse, la séparation de phase dans les aluminosilicates de calcium étant visible à l’échelle macroscopique, nous voulions donc suivre la diminution de la séparation de phase avec l’ajout d’alumine. Ainsi, en élaborant un protocole de synthèse spécifique, nous avons pu synthétiser ces verres à hautes températures. Ils ont été étudiés par le biais de la microscopie électronique et de la RMN. Comme ces verres sont composés de nano-domaines vitreux intégrés dans une matrice de composition différente, nous avons pu obtenir des matériaux nano-structurés de taille contrôlée. L’utilisation de la RMN nous a permis de montrer que l’aluminium s’insérait sous forme de « clusters » dans le réseau silicaté. / The understanding of the vitreous state is actually a center of great interest in inorganic chemistry. In fact, even if a glass is often described as a totally disordered material, presence of structures at the atomic scale has to be considered. One of the first experimental proof against the random network theory is the observation of phase separation. In fact, in these systems, at least two glasses with different compositions are observed. In this way, the first steps of phase separation in sodium silicate glasses have been studied. This was afforded with the NMR technique using 29Si-29Si correlations experiments. Thus, the silicon network was probed at higher distances compared with which was commonly observed in these glasses. Therefore, we have been able to identify this phenomenon at the atomic scale, to define the composition of each glassy phase and to do a link with crystallization which happened after long heat treatment of the glass. At the contrary phase separation in calcium aluminosilicate glasses can be observed at the macroscopic scale, observation of its decrease with increasing amount of alumina has been under the scope of this study. The main challenge of this study was to synthesized high temperature glasses. Since an efficient protocol has been implemented, we have been able to obtained nano-structured materials with a controlled size of nano-domains. This caracterisation of the material has been possible using electron microscopy. Combined with NMR, we have been able to propose a mechanism to explain insertion of alumina in the silicon network.

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Orientadores: Teresa Massako Kakuta Ravagnani, Leila Peres / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-18T23:18:07Z (GMT). No. of bitstreams: 1 Araujo_PauloJardelPereira_D.pdf: 15740528 bytes, checksum: bd5969744efcacfde55b69c10f951f33 (MD5) Previous issue date: 2011 / Resumo: O biodiesel além de ser biodegradável e obtido de fontes renováveis, apresenta propriedades físico-químicas muito semelhantes ao diesel de petróleo, não necessitando de um novo motor para utilização do mesmo. A rota química mais comumente usada para obtenção do biodiesel é a transesterificação. Nesta, pela reação de um álcool com os triacilgliceróis (TAG) presentes principalmente em óleos vegetais e gordura animal, são produzidos o biodiesel e, como produto secundário, o glicerol em grandes quantidades. A presença deste glicerol é indesejada, pois além de diminuir a produtividade do biodiesel pelo equilíbrio termodinâmico estabelecido no processo, também aumenta seu custo pelo alto tempo de decantação e/ou uso de centrífugas para remover o glicerol do biodiesel. Devido a este inconveniente, o presente trabalho propõe rota alternativa para separação do glicerol, utilizando membrana de microfiltração (TiO2/Al2O3). Vários sistemas foram analisados, focando a separação do glicerol, o aumento do fluxo permeado e da conversão de TAG na catálise heterogênea. Inicialmente estudou-se a permeabilidade e seletividade dos reagentes e produtos obtidos na síntese do biodiesel com a membrana, através de experimentos binários. A partir destes resultados, estabeleceu-se uma nova configuração do sistema para então analisar estes fatores em misturas compostas pelos quatro constituintes do processo através de um planejamento fatorial. Os resultados apresentados geraram modelos que descrevem com 95% de confiabilidade o coeficiente de rejeição ao glicerol e o fluxo permeado frente aos fatores analisados (nível de emulsificação, razão molar óleo/etanol e conversão de TAG). Selecionou-se então, uma melhor faixa destes fatores que resultem em um máximo de rejeição ao glicerol com máximo fluxo permeado, obtendo um resultado bastante representativo do processo que apresentou um bom fluxo permeado (90,11kg/h.m2) com alta rejeição de glicerol (98,69%). Posteriormente propôs-se um estudo do processo simultâneo de reação e separação (leito fixo catalítico envolto em membrana), sendo selecionado para a reação de síntese um catalisador heterogêneo (SrO suportado em alumina), visando facilitar o processo de separação e reduzir significativamente o número de etapas de purificação dos produtos. Os resultados de conversão do TAG foram baixos, impossibilitando uma análise completa do sistema com esta configuração do ponto de vista de reação e separação concomitante / Abstract: In addition to being biodegradable and renewable, Biodiesel presents physicochemical properties very similar to those of petroleum-based diesel, so a new engine is not required for its use. The most commonly used chemical process for obtaining biodiesel is transesterification. In this process, through the reaction of an alcohol with triacylglycerols (TAG) present mainly in vegetable oils and animal fat, biodiesel is formed with large quantities of glycerol as a byproduct. The presence of glycerol is unwanted because besides reducing the productivity of biodiesel through the thermodynamic equilibrium established in the process, it also increases the cost due to the long time for settling and/or use of centrifuges for removing the glycerol from biodiesel. Taking into account this inconvenience, this paper proposes an alternative process for the separation of glycerol, using TiO2/Al2O3 membranes. Various systems were analyzed, focusing on the separation of glycerol, the increase of the permeate flux, and the increase in the TAG productivity in heterogeneous catalysis. At first we studied the permeability and selectivity of reagents and products obtained in the biodiesel synthesis with a membrane through binary experiments. From these results a new configuration of the system was established, with subsequent analysis of the new interaction in mixtures of the four components of the process (oil, Ethanol, Biodiesel, glycerol) using a factorial design as tool. Results presented in the factorial design generated models that describe with 95% reliability the glycerol rejection coefficient and the permeate flux compared to the analyzed factors (level of emulsification, molar ratio of oil/ethanol and TAG conversion). A best range of factors that result in a maximum glycerol rejection with maximum permeate flux was selected, obtaining a fairly representative result of the process showing a good permeate flux (90.11 kg/h.m2) with high glycerol rejection rate (98.69%). Subsequently, the study of the reaction and separation simultaneous process was proposed (fixed catalytic bed involved in a membrane) selecting an heterogeneous catalyst (SrO on alumina) to facilitate the separation process and significantly reduce the number of purification steps of products. Results of biodiesel conversion were low, preventing a full assessment of the system with this configuration considering simultaneous reaction and separation / Doutorado / Sistema de Processos Quimicos e Informatica / Doutor em Engenharia Química

Gas absorption in hollow fibre contactors is being increasingly used due to their enormous surface area/volume ratio. The capability of the hollow fibre membrane modules for the removal of CO 2 and SO2 from a binary gas mixture has been investigated experimentally. Four different modules were used in this study. The membranes in modules one and two were made of microporous polypropylene. The third module was made of non-porous silicone rubber (polydimethylsiloxane) while the latter one was a polyvinylidenefluoride (PVDF) asymmetric hollow fibre membrane. The gas mixtures used in the experiments were composed of 9.5% CO2 and 1% SO2 in N 2 , which was introduced into the hollow fibre lumen, while the absorbent liquid was fed into the shell side of module. The absorbent liquids used were water, aqueous solutions of diethanolamine (DBA) and ammonia at different concentrations (5, 10 and 20 wt%). The effects of different operating conditions on the permeation process have been investigated for co-current and counter-current flow patterns. In addition, to improve the silicone rubber hollow fibre membrane performance, baffles were installed within the shell of the permeator to increase liquid fibre contact. The results obtained showed that the use of baffles within the shell of the permeator improved the separation performance of the non-porous membrane module without any substantial increase in the physical size of the contacting device. Studies also showed that improved performance was observed when the system was operated under a counter-current flow pattern. The results showed that the use of an absorbent liquid in the permeate side of the fibres increased the selectivity of the membranes used, and reduced the need to maintain a high pressure ratio across the membrane. A decrease in the feed gas flow rate or increase in liquid flow rate generally improved the removal of gases. The results showed that the use of aqueous reactive solutions as an absorbing medium in the permeate side of the hollow fibre permeator can significantly improve CO2 removal from the gas mixture. However, the main problem when using a microporous membrane coupled with aqueous solutions of diethanolamine as absorbent was wetting of the microporous membrane by amine solutions. For 862 separation, the highest removal was attained using the microporous membrane coupled with water as absorbent liquid. This demonstrates that a hollow fibre based device can be a very efficient gas liquid contactor. The separation process was simulated with a numerical model based on the effective permeabilities of gases and compared with the experimental results. The model simulations showed good agreement with the experimental observations.

In this dissertation, the aim was to develop a platinum specific resin to be utilized for the early removal of platinum from the industrial feed solution. Efforts were therefore directed towards the syntheses of silica based resins, with active centra, designed for platinum. The large chlorometallate ions present in the feed stream, were characterized in terms of physical parameters relevant to phase distribution, namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins, different structural amines were used to aminate the silicone precursor and to subsequently fix these onto the silica framework. Two different solvents namely alcohol and dmf were used in this process, resulting in two sets of resins, with different properties. The design was based on previous experience with these ions, with reference to their behaviour towards different types of cations. The platinum species, PtCl6 2- and PtCl4 2-, as well as the most important contaminants in the feed stream, were typified, bearing in mind size, charge, charge density and distortability. Different types of cationic centra, having differences in charge density, stereochemical crowding and extent of hydrophobicity, were synthesized and tested-both as solvent extractants (where possible) and silica based resins. The results indicated that, partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was however necessary, to work at a redox potential, where iridium(IV) in the form of IrCl6 2-, was absent. Various 2-aminoalkane resins were prepared, with variation in the length of alkane group and synthesised by the two different solvents. The latter resulted in two sets of resins with not only differing compactness, but also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2-aminobutane and 2-aminoheptane resins in particular, proved to be very satisfactory platinum specific resins, both with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be applied to identify the chemical behaviour of anions and assist in the development of anion specificity for the relevant species.

No description available.

The Centrifugal Membrane and Density Separation (CMDS) process is a novel type of membrane process that exploits the action of a centrifuge to generate process pressure for reverse osmosis and nanofiltration. The centrifuge could potentially enhance flux and alleviate fouling of the membrane as a result of the hydrodynamic environment of the centrifuge. All experimental work has been conducted on a prototype model of the CMDS process. The apparatus allows a membrane module to be fixed in space at a specified orientation, with respect to the rotation. This orientation in space is denoted by the terms “pitch, roll and yaw” (p,r,y). Experiments have been done using brine feed solutions at various concentrations to determine if the CMDS process minimizes the effects of concentration polarization. An example of this was illustrated with a 54% flux enhancement relative to a conventional membrane process using a 35000 ppm NaCl feed solution. Colloidal feed solutions were also used to examine how the CMDS process enhances flux in a fouling environment. These feed solutions include 21 g/L silica and 300 mg/L humic acid, with typical relative flux enhancement factors (κ) found to be 0.59 and 0.14, respectively. The final group of experiments examined the use of 50 g/L whey feed solutions with nanofiltration membranes. Results obtained here indicate that the centrifugal action enhanced the flux with an absolute flux enhancement factor (κ′) of 17.5 L/m² hr. These experiments have shown that a given orientation (90,270,0) best enhances the flux of a membrane with respect to colloidal fouling, while showing that another orientation (90,180,0) best reduces the effects of concentration polarization. Scanning electron microscopy (SEM) and an energy dispersive x-ray (EDX) detector have helped to examine the nature of the fouling layers and determine how well the layers adhere to the surface of the membrane. It was determined that in some cases, the fouling layer adhered better to the surface of a membrane used in the CMDS process. However, as the fluxes were typically higher in the dynamic process, it leads to the conclusion that the fouling layer on the CMDS membranes is more permeable. From the experimental work it has been concluded that the forces at work in the CMDS process create sufficient secondary flow instabilities to reduce the effects of fouling and concentration polarization on the membrane surface. The significance of this process with respect to industrial applications is considered, and the process is deemed feasible for such applications. / Graduate

Backmixing of the continuous phase was studied in liquid-liquid spray columns of various geometries, for various flowrates of the two phases, and for various drop size distributions. The dispersion or eddy diffusion model was used to characterize the axial mixing of the continuous phase. Axial concentration profiles were measured upstream, with respect to the continuous phase, from a distributor of sodium chloride tracer (soluble in the continuous phase only). The steady state form of the model was utilized to calculate axial eddy diffusivities from these results. The tracer studies showed that the axial eddy diffusivity is independent of the continuous phase flowrate and the column height. Axial eddy diffusivities between 7-ft.²/hr. and 31-ft.²/hr. were obtained in a 1½-in. I. D. column. Low dispersed phase flowrates and large drop sizes resulted in high axial eddy diffusivities. Increasing the column diameter to 3-in. resulted in superficial axial eddy diffusivities between 6.3 and 17.3 times larger. The hold-up of dispersed phase was measured by means of a piston sampler. The hold-up increases approximately linearly with increasing dispersed phase superficial velocity and tends to be slightly higher for increased continuous phase superficial velocities. A smaller drop size resulted in an increased hold-up. Drop size distributions were measured. They always show two peaks, one at 0.02-in. diameter, and the other at a much larger size, the actual value of which depends on the nozzle tip diameter used to disperse the drops. The mixing cell-packed bed analogy was used to predict Peclet numbers in a spray column. The agreement between these and measured Peclet numbers is good for drops of about 0.15-in. equivalent diameter but becomes progressively worse as the drop size is reduced. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

An experimental investigation was undertaken to study the factors affecting phase separation in a specially constructed, laboratory scale mixer-settler. Two phase systems were used: 1. A laboratory prepared HSLIX64N-copper phase system, similar to that used in commercial copper solvent extraction processes. 2. A phase system obtained directly from the uranium extraction circuit of the Key Lake Mining Corporation, Sask., millsite. A settler scale-up criterion relating dispersion band thickness to specific settler flow of dispersed phase, was found to have considerable merit. Besides being dependent on specific settler flow, the dispersion band thickness was found to be a function of the phase ratio (for system 2 only), dispersion introduction level (for system 2 only), and temperature. Mixing intensity had no appreciable effect with either system. Microscopic examination of the dispersion produced with system 2 revealed the existence of double dispersions; that is, drops within drops. A photomicroscopic technique was used to undertake a drop size investigation of the dispersion produced with system 2. Drop size was found to be independent of dispersion throughput, a weak function of impellor speed and a relatively strong function of the phase ratio. With the exception of organic continuous operation with system 1, it was possible, based on the holdup and drop size profile within the dispersion band, to distinguish two horizontal sublayers within the dispersion band. In the "even concentration sublayer", comprising the majority of the dispersion band, the holdup and average drop size is nearly constant throughout. In the "dense concentration sublayer", both the holdup and the average drop size increase sharply as the coalescence front is approached. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate