Made available in DSpace on 2014-10-09T12:31:33Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:25Z (GMT). No. of bitstreams: 1 02291.pdf: 2482400 bytes, checksum: 32eba3e165bfda2741408d2c09c40418 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:37:28Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:31Z (GMT). No. of bitstreams: 1 02046.pdf: 4605414 bytes, checksum: 083bd884df538642741b4cf2176f8795 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:31:59Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:15Z (GMT). No. of bitstreams: 1 02571.pdf: 2380291 bytes, checksum: 94e6be3db24a9f0c5c1f13277cd435f2 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:31:33Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:25Z (GMT). No. of bitstreams: 1 02291.pdf: 2482400 bytes, checksum: 32eba3e165bfda2741408d2c09c40418 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:37:28Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:31Z (GMT). No. of bitstreams: 1 02046.pdf: 4605414 bytes, checksum: 083bd884df538642741b4cf2176f8795 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Na otimização do refino de petróleo é fundamental predizer a distribuição dos produtos e sua qualidade. O petróleo é uma substância muito complexa e é praticamente impossível caracterizá-lo de maneira usual, analisando a quantidade de cada um dos seus constituintes. Portanto, convencionalmente, ele é caracterizado por métodos baseados na análise da destilação, tais como o ensaio de destilação chamado de True Boiling Point (TBP) e o ensaio ASTM D86. Para predizer a distribuição dos produtos e sua relação com as condições de funcionamento, simulações em estado estacionário baseadas em primeiros princípios, em termos de balanços de massa, energia e relações de equilíbrio, são extremamente importantes. Como o número de componentes no petróleo é muito elevado a composição da mistura não pode ser utilizada diretamente. Convencionalmente, dezenas de pseudocomponentes são geradas, a fim de representar o petróleo. Mais recentemente, foi proposta a aproximação do petróleo por um conjunto reduzido de componentes reais. É esta abordagem que é estudada nesta dissertação. O principal desafio deste método é a determinação dos componentes reais e das suas quantidades, que são escolhidos para representar a mistura original. Na metodologia para a seleção da mistura substituta é necessário simular as curvas de destilação disponíveis experimentalmente. Neste trabalho simulamos as curvas de destilação TBP e ASTM D86 dentro do ambiente BatchSep da Aspentech. São apresentadas aplicações destas simulações em seis exemplos diferentes. Destes exemplos cinco se referem à simulação da TBP e um à ASTM D86. Alguns exemplos são baseados em misturas com composição conhecida, e em outros há comparações com dados experimentais de cortes de petróleo. A metodologia da mistura substituta e a dos pseudocomponentes foram comparadas na simulação de uma coluna de destilação. De maneira geral a metodologia proposta na literatura é adequada quando se quer representar a curva de temperatura apenas. Quando se dispõe de dados de densidade o método fica limitado pela disponibilidade de componentes na base de dados e pela hipótese de que os componentes saem puros, um a um, que é feita ao se adotar a metodologia convencional. Uma metodologia que leva em conta o fato de que os cortes são uma mistura de componentes deve ser implementada para que o método seja tecnicamente atraente. / In the process of optimizing petroleum refining, it is essential to predict the distribution of products and their quality. Petroleum is a very complex substance and it is practically impossible to characterize it in the usual manner, by analyzing the quantity of each single component. Therefore, conventionally, it is characterized by methods based on the analysis of distillation, such as the True Boiling Point (TBP) distillation test and the ASTM D86 test. In order to predict the distribution of products and their relationship with the operating conditions, stationary state simulations based on primary principals, in terms of fluctuations of mass, energy and relations of balance, are extremely important. As the number of components in petroleum is very high, the composition of the mixture cannot be used directly. Conventionally, dozens of pseudocomponents are created, in order to simulate petroleum. More recently the approximation of petroleum through a reduced set of real components has been proposed. This is the approach studied in this dissertation. The main challenge of this method is the determination of the real components chosen to simulate the original mixture, and their quantities. It is necessary to simulate the available distillation curves experimentally in the methodology for the selection of the substitute mixture. In this study, we simulated the TBP and ASTM D86 distillation curves in an Aspentech BatchSep environment. Applications of these simulations are presented in six different examples. Of these examples, five are TBP simulations and one is an ASTM D86 simulation. Some examples are based on mixtures with known compositions, and in others there are comparisons with experimental data from petroleum samples. The methodology of the substitute mixture and that of the pseudo-components were compared in the simulation of a distillation column. In general, the methodology proposed in literature is suitable when the only simulation that is required is a temperature curve. When density data is available, the method becomes limited by the availability of components in the data base and by the hypothesis that the components emerge pure, one by one, which is what happens when conventional methodology is adopted. A methodology that takes into account the fact that the samples are a mixture of components must be implemented so that the method is technically appealing

Rare earth elements (REEs) are a group of 15 elements in the lanthanide series along with scandium and yttrium. They are often grouped together because of their similar chemical properties. As a result of their increased application in advanced technologies and electronics including electric vehicles, the demand of REEs and other critical elements has increased in recent decades and is expected to significantly grow over the next decade. As the majority of REEs are produced and utilized within the manufacturing industry in China, concerns over future supplies to support national defense technologies and associated manufacturing industries has generated interest in the recovery of REEs from alternate sources such as coal and recycling. A solvent extraction (SX) process and circuit was developed to concentrate REEs from dilute pregnant leach solutions containing low concentrations of REEs and high concentrations of contaminant ions. The separation processes used for concentrating REEs from leachates generated by conventional sources are not directly applicable to the PLS generated from coal-based sources due to their substantially different composition. Parametric effects associated with the SX process were evaluated and optimized using a model test solution produced based on the composition of typical pregnant leach solution (PLS) generated from the leaching of pre-combustion, bituminous coal-based sources. Di-2(ethylhexyl) phosphoric acid (DEHPA) was used as the extractant to selectively transfer the REEs in the PLS from the aqueous phase to the organic phase. The tests performed on the model PLS found that reduction of Fe3+ to Fe2+ prior to introduction to the SX process provided a four-fold improvement in the rejection of iron during the first loading stage in the SX circuit. The performances on the model system confirmed that the SX process was capable of recovering and concentrating the REEs from a dilute PLS source. Subsequently, the process and optimized parametric values were tested on a continuous basis in a pilot-scale facility using PLS generated from coal coarse refuse. The continuous SX system was comprised of a train of 10 conventional mixer settlers having a volume of 10 liters each. A rare earth oxide (REO) concentrate containing 94.5% by weight REO was generated using a two- stage (rougher and cleaner) solvent extraction process followed by oxalic acid precipitation. The laboratory evaluations using the model PLS revealed issues associated with a third phase formation. Tributyl Phosphate (TBP) is commonly used as a phase modifier in the organic phase to improve the phase separation characteristics and prevent the formation of a third phase. The current study found that the addition of TBP affected the equilibrium extraction behavior of REE as well as the contaminant elements., The effect on each metal was found to be different which resulted in a significant impact on the separation efficiency achieved between individual REEs as well as for REEs and the contaminant elements. The effect of TBP was studied using concentrations of 1% and 2% by volume in the organic phase. A Fourier Transform Infrared (FTIR) analysis on the mixture of TBP and DEHPA and experimental data quantifying the change in the extraction equilibrium for each element provided insight into their interaction and an explanation for the change in the extraction behavior of each metal. The characteristic peak of P-O-C from 1033 cm-1 in pure DEHPA to 1049 cm-1 in the 5%DEHPA-1%TBP mixture which indicated that the bond P-O got shorter suggesting that the addition of TBP resulted in the breaking of the dimeric structure of the DEHPA and formation of a TBP-DEHPA associated molecule with hydrogen bonding. The experimental work leading to a novel SX circuit to treat dilute PLS sources was primarily focused on the separation of REEs from contaminant elements to produce a high purity rare earth oxide mix product. The next step in the process was the production of individual REE concentrates. To identify the conditions needed to achieve this objective, a thermodynamic model was developed for the prediction of distribution coefficients associated with each lanthanide using a cation exchange extractant. The model utilized the initial conditions of the system to estimate the lanthanide complexation and the non-idealities in both aqueous and organic phases to calculate the distribution coefficients. The non-ideality associated with the ions in the aqueous phase was estimated using the Bromley activity coefficient model, whereas the non-ideality in the organic phase was computed as the ratio of the activity coefficient of the extractant molecule and the metal extractant molecule in the organic phase which was calculated as a function of the dimeric concentration of the free extractant in the organic phase. To validate the model, distribution coefficients were predicted and experimentally determined for a lanthanum chloride solution using DEHPA as the extractant. The correlation coefficient defining the agreement of the model predictions with the experimental data was 0.996, which is validated the accuracy of the model. As such, the developed model can be used to design solvent extraction processes for the separation of individual metals without having to generate a large amount of experimental data for distribution coefficients under different conditions.

No description available.

Le complexe SAGA (Spt-Ada-Gcn5 acetyl transferase) est un co-activateur transcriptionel, conservé chez les eucaryotes, qui participent à la transcription d’environ 10% des gènes chez la levure, où il fait le lien entre les composants du complexe de pré-initiation, tel que la TATA-box Binding Protein (TBP) et des activateurs, et modifie les histones dans le contexte de la chromatine (acétylation et déubiquitination). Ces travaux de thèse ont permis de décrire l’architecture moléculaire du complexe observée par microscopie électronique. Nous avons pu (i) localiser le module de déubiquitination au sein du complexe entier et ainsi (ii) définir une zone d’interaction avec le nucléosome ; (iii) montrer la présence de deux sites d’interaction avec la protéine TBP situé au niveau d’une « pince »moléculaire ; (iv) observer un lien fonctionnel entre le module de déubiquitination, en particulier de la protéine Sgf73, et les conformations adoptées par cette pince. / The SAGA complex (Spt-Ada-Gcn5 acetyl transferase) is a transcriptional coactivator, highly conserved in eukaryotes, involved in the transcription of 10% of the genes in yeast, where it bridges the components of the pre-initiation complex such as the TATA-box Binding Protein (TBP) and activators, as well as modifies histones in the chromatin template (acetylation and deubiquitination). This work has revealed the molecular architecture of the complex observed by electron microscopy. We could (i) localize the deubiquitination module within the whole complex and thus (ii) define the interaction surface with the nucleosome; (iii) reveal the presence of two TBP-interacting surfaces localized at the tips of a molecular clamp; (iv) observe a functional link between the deubiquitination module, in particular the Sgf73 protein, and the conformation adopted by this clamp.

No description available.