[pt] A degradação do meio ambiente está no topo da agenda de países e empresas. O foco principal é a redução das emissões de gases causadores do efeito estufa, sendo CO2 o maior contribuinte. O consumo elevado de combustíveis fósseis está criando um efeito irreversível no planeta. De forma a contrabalancear seus impactos ambientais, surge o segmento de projetos de captura e sequestro de carbono. O maior entrave seu para crescimento é econômico, daí o uso de CO2 para recuperação avançada de óleo, alavancando sua implementação. Esta dissertação avalia duas estratégias distintas de desenvolvimento de um campo de petróleo offshore, uma através da injeção de água e outra por recuperação avançada com injeção de CO2 (EOR CO2 – enhanced oil recovery) a partir de fonte antropogência. Os maiores desafios técnicos para aplicação de EOR CO2 em ambiente offshore são examinados, mostrando o arcabouço teórico, melhores práticas e soluções ainda não desenvolvidas, em áreas como: gerenciamento de reservatórios, engenharia de poços e plantas de processo, além de captura e transporte de CO2. Em seguida, a viabilidade econômica de ambos os métodos de recuperação são comparados, com pequena vantagem o caso EOR. Entretanto, devido às incertezas de sucesso do método e sua sensibilidade ao preço de importação de CO2, a gama de resultados pode alterar o processo decisório. Um balanço de carbono também é realizado, mostrando a redução esperada de sua concentração na atmosfera ao se selecionar o método de EOR CO2. Ainda, a aplicabilidade de créditos de carbono é discutida, e seu impacto econômico quantificado. Finalmente, há um longo caminho a se percorrer para ampla utilização de projetos EOR com CO2 antropogênico em ambiente offshore. Ao apontar os maiores desafios e entraves a serem superados, incluindo técnicos, comerciais e regulatórios, ao apresentar modelo econômico, e acima de tudo, ao mostrar sua atratividade, esta dissertação tem por objetivo reduzir esta distância. / [en] Environmental issues are on top of governments and companies’ agendas. The main focus is on global warming and means to reduce greenhouse gases, being carbon dioxide the main contributor. The consumption of fossil fuels is creating an irreversible effect on the planet, and it is expected to continue for years to come. In order to offset its usage are the emerging carbon capture and storage (CCS) projects. Their main obstacle is economical, and that’s where enhanced oil recovery through CO2 can help. This dissertation assesses the development options of an offshore Brazilian discovery, by comparing water injection method with carbon dioxide enhanced oil recovery (EOR CO2) imported from an anthropogenic onshore source. The main EOR CO2 technical challenges for offshore application are examined, detailing field proven and yet to be developed solutions, from reservoir management, wells engineering to the production unit, passing through CO2 acquisition and transportation. Next, economical feasibility of both methods are compared, with a slight advantage for EOR on the base case. Nevertheless, due to high uncertainties in method success prior to development and commitment, and also to carbon dioxide import prices, the range of results can shift the decision making, and such sensitivity analysis is also presented. A carbon inventory is also made, showing the net positive balance of selecting EOR CO2, which reduces the component’s concentration in the atmosphere. Finally, the applicability of carbon credits is discussed and its economical impact quantified. There is still a long way to go for the widespread utilization of anthropogenic EOR CO2 in offshore projects. By pointing out the main challenges to be addressed, including technical, commercial and regulatory, by presenting an economical model comprising environmental aspects, and most of all, showing its attractiveness, this dissertation aims to reduce this gap.

Using a hydrogen donor and a catalyst for upgrading and increasing oil recovery during in situ combustion is a known and proven technique. Based on research conducted on this process, it is clear that widespread practice in industry is the usage of tetralin as a hydrogen donor. The objective of the study is to find a cheaper hydrogen donor with better or the same upgrading performance. Decalin (C10H18) is used in this research as a hydrogen donor. The experiments have been carried out using field oil and water saturations, field porosity and crushed core for porous medium. Four in situ combustion runs were performed with Gulf of Mexico heavy oil, and three of them were successful. The first run was a control run without any additives to create a base for comparison. The next two runs were made with premixed decalin (5 percent by oil weight) and organometallic catalyst (750 ppm). The following conditions were kept constant during all experimental runs: air injection rate at 3.1 L/min and combustion tube outlet pressure at 300 psig. Analysis of the performance of decalin as a hydrogen donor in in-situ combustion included comparison of results with an experiment where tetralin was used. Data from experiments of Palmer (Palmer-Ikuku, 2009) was used for this purpose, where the same oil, catalyst and conditions were used. Results of experiments using decalin showed better quality of produced oil, higher recovery factor, faster combustion front movement and higher temperatures of oxidation. API gravity of oil in a run with decalin is higher by 4 points compared to a base run and increased 5 points compared to original oil. Oil production increased by 7 percent of OOIP in comparison with base run and was 2 percent higher than the experiment with tetralin. The time required for the combustion front to reach bottom flange decreased 1.6 times compared to the base run. The experiments showed that decalin and organometallic catalysts perform successfully in in situ combustion, and decalin is a worthy replacement for tetralin.

[pt] O sequestro de dióxido de carbono (CO2) em campos de petróleo já desenvolvidos é considerado uma das opções para mitigar o CO2 antropogênico expelido na atmosfera. O CO2 tem sido utilizado como fluido de injeção em operações de recuperação avançada de petróleo com CO2 (CO2-EOR). Como parte deste processo, o CO2 reage com o óleo que expande seu volume, reduz sua viscosidade e a tensão interfacial CO2/óleo, tornando mais fácil sua recuperação. Enquanto, quantidades significativas de CO2 ficam retidas no reservatório. O objetivo desses projetos é maximizar a produção de óleo, minimizando a injeção de CO2. No entanto, em projetos de sequestro para maximizar a produção de óleo com a maior quantidade de armazenamento de CO2, o gás injetado requer ser maximizado. O objetivo desta pesquisa é entender melhor o potencial tanto para a recuperação avançada de óleo e armazenamento de CO2, por meio da simulação da CO2-EOR. Para atingi-lo propõe-se os seguintes objetivos específicos: (1) caracterização dos fluidos, modelagem do comportamento de fases dos fluidos usando a equação de estado (EOS) para aplicação confiável na simulação composicional; (2) investigar diferentes processos EOR, injeção contínua de gás (CGI) e injeção alternada de água e gás (WAG); e, (3) otimização do desempenho do processo CO2-EOR e a avaliação da capacidade de armazenamento de CO2 durante a produção de óleo. Os seguintes parâmetros foram considerados no estudo da otimização: i) miscibilidade; ii) a injeção cíclica; iii) a taxa de injeção e produção; iv) segregação gravitacional; v) tipo, número e locação dos poços de injeção e produção; e, vi) razão de WAG e tamanhos dos slugs. São necessárias um grande número de simulações para alcançar uma compreensão abrangente e avaliar as diferentes estratégias de injeção e tempo de injeção, em otimização de recuperação de óleo e capacidade de armazenamento de CO2. / [en] Sequestration of carbon dioxide (CO2) into already developed oil fields is considered as one of the option for mitigating anthropogenic CO2 discharge into the atmosphere. In Carbon dioxide Enhance Oil Recovery (CO2-EOR) operations the CO2 has been used as the injection fluid. As part of this process, the CO2 reacts with the oil that increases its volume, reduces its viscosity and interfacial tension CO2/oil, making easier oil recovery. While, significant quantities of CO2 remain sequestered in the reservoir. The goal of such projects is maximizing the oil production and minimizing the CO2 injection. However, in sequestration projects, for maximum oil production with the highest amount of CO2 storage, the injected CO2 requires to be maximized. The goal of this research is to better understand the potential for both enhanced oil recovery and storage of CO2, through the CO2-EOR simulation. To achieve it propose the following specific objectives: (1) the characterization fluids, modeling of fluid phase behavior using equation of state (EOS) for reliable application on the compositional simulation; (2) investigate different EOR processes, continuous gas injection (CGI) and water alternating gas (WAG) injection; and, (3) optimization the CO2-EOR process performance and evaluation of the CO2 storage capacity during oil production. The following parameters were considered in the optimization study: i) miscibility; ii) cyclic injection; iii) injection and production rate; iv) gravity override; v) type, number and location of injection and production wells; and, vi) WAG ratios and WAG slug sizes. A number of simulations are required to achieve comprehensive understanding and evaluate the different injection strategies and injection timing, on optimization of oil recovery and CO2 storage capacity.

Made available in DSpace on 2014-12-17T15:01:47Z (GMT). No. of bitstreams: 1 TulioYFV_D.pdf: 3087566 bytes, checksum: 98d82de1a3cf355e814daf66c053ad55 (MD5) Previous issue date: 2009-07-10 / The high concentration of residual oil is one of the greatest problems found in petroleum mature fields. In these reservoirs, different enhanced oil recovery methods (EOR) can be used, highlighting the microemulsion injection. The microemulsion has showed to be efficient in petroleum recovery due to its ability to promote an efficient displacement of the petroleum, acting directly in the residual oil. In this way, this research has as objective the study of microemulsion systems obtained using a commercial surfactant (TP), determining microemulsion thermal stabilities and selecting points inside the pseudoternary phases diagram, evaluating its efficiencies and choosing the best system, that has the following composition: TP as surfactant (S), isopropyl alcohol as co-surfactant (C), kerosene as oil phase, water as aqueous phase, C/S ratio = 1, and 5% sodium p-toluenesulfonate as hydrotope; being observed the following parameters for the selection of the best pseudoternary phases diagram: C/S ratio, co-surfactant nature and addition of hydrotope to the system. The efficiency in petroleum recovery was obtained using two sandstone formation systems: Assu and Botucatu. The study of thermal stabilities showed that as the concentration of active matter in the system increased, the thermal stability also increased. The best thermal stability was obtained using point F (79.56 0C). The system that presented the best recovery percentile between the three selected (3) was composed by: 70% C/S, 2% kerosene and 28% water, with 94% of total recovery efficiency and 60% with microemulsion injection, using the Botucatu formation, that in a general way presented greater efficiencies as compared with the Assu one (81.3% of total recovery efficiency and 38.3% with microemulsion injection) / Um dos grandes problemas encontrados nos campos maduros ? a alta satura??o de ?leo residual. Nesses campos, a inje??o de microemuls?o pode ser utilizada na recupera??o de petr?leo, pois esta tem se mostrado eficiente na recupera??o de petr?leo devido ? obten??o de um deslocamento eficiente do petr?leo, atuando diretamente no ?leo residual. Esse trabalho tem como objetivo estudar sistemas microemulsionados para a recupera??o de petr?leo, determinando suas estabilidades t?rmicas e avaliando suas efici?ncias de recupera??o. Os sistemas microemulsionados selecionados foram obtidos escolhendo-se pontos no diagrama de fases, com a seguinte composi??o: co-tensoativo, ?lcool iso-prop?lico (raz?o C/T=1), querosene, tensoativo (TP) e 5% de ptoluenosulfonato de s?dio (hidr?tropo). Para a escolha desse diagrama de fases foram avaliadas: a raz?o C/T, o co-tensoativo e a adi??o de hidr?tropo ao sistema. As forma??es estudadas na recupera??o de petr?leo foram: a Assu e a Botucatu. O estudo das estabilidades t?rmicas do sistema apontou que ? medida que se aumentou a concentra??o de mat?ria ativa, aumentava-se a estabilidade t?rmica do mesmo. A maior estabilidade t?rmica foi obtida no ponto F (79,56 0C). Dos pontos selecionados (3) o sistema que apresentou o maior percentual de recupera??o foi obtido com o sistema constitu?do de 70% C/T, 2% de querosene e 28% de ?gua, levando a 94 % de efici?ncia total e 60% de inje??o de microemuls?o, utilizando-se a forma??o Botucatu, que no geral apresentou efici?ncias maiores do que a forma??o Assu (81,3 % de efici?ncia total e 38,3% com microemuls?o)

[pt] Os métodos de recuperação terciária ou avançada de petróleo (EOR) permitem fatores de recuperação de até 70 por cento. A injeção de surfactantes aniônicos, amplamente empregados em EOR químico, pode se tornar inviável devido às perdas após precipitação, difusão para o interior de poros sem conectividade e especialmente adsorção sobre a superfície da rocha reservatório. Este trabalho almejou modificar a superfície de nanopartículas de sílica com alcoxisilanos para que possam ser utilizadas como nanocarreadores de surfactantes aniônicos em EOR químico, diminuindo desta forma as perdas por adsorção. Técnicas de caracterização foram empregadas para confirmar a modificação ocorrida na superfície da sílica, obtendo-se graus de modificação estimados entre 11 e 14 por cento. A inserção de grupos alquila (C8 e C16) na superfície da sílica aumentou significativamente a interação com o surfactante aniônico (dodecil sulfato de sódio, SDS), em comparação com as nanopartículas sem modificação, ampliando em até 11x a quantidade de surfactante retido na superfície das nanopartículas. Os nanomateriais híbridos obtidos possuem maior capacidade de manter adsorvido o tensoativo em soluções aquosas e salinas, bem como liberá-lo quando na interface salmoura/óleo. Ao fim, as nanopartículas de sílica modificadas contendo surfactante adsorvido na sua superfície atuaram sinergicamente na redução da tensão interfacial, sem afetar o desempenho do surfactante após liberação na interface água/óleo. Sendo assim, as nanopartículas modificadas com alcoxisilanos obtidas neste trabalho podem atuar como nanocarreadores de surfactantes em fluidos de injeção para EOR químico. / [en] The tertiary oil recovery methods or enhanced oi recovery (EOR) allow a recovery factor up to 70 percent. The injection of anionic surfactants, widely used in chemical EOR, could become unfeasible due to losses after precipitation, diffusion to the interior of non-connected pores and specially adsorption over reservoir rock surface. This work aimed to modify the surface of silica nanoparticles with alkoxysilanes in order to be used as surfactant nanocarriers in chemical EOR, reducing surfactant loss by adsorption. Characterization techniques were employed to confirm the modifications on silica surface, obtaining degrees of modification between 11 and 14 percent. The attachment of alkyl groups (C8 and C16) on the silica surface raised significantly the interaction with an anionic surfactant (sodium dodecyl sulfate, SDS), in comparison to bare silica nanoparticles, increasing up to 11x the amount of adsorbed surfactant over silica s surface. The hybrid nanomaterials obtained in this work have a high capacity to keep the tensoactive in aqueous solutions and brine, as well as releasing it at the brine/oil interface. Finally, the modified silica nanoparticles containing surfactant adsorbed on their surface showed a synergy in reducing interfacial tension, without affecting the surfactant performance after the release at the water/oil interface. Thus, the nanoparticles modified with alkoxysilanes obtained in this work can act as surfactant nanocarriers in injection fluids for chemical EOR.

Inhalt der Arbeit sind theoretische und experimentelle Untersuchungen zum Einfluss akustischer Wellen auf das Verhalten mehrphasiger Strömungen in porösen Medien. Die Arbeit schlug mittels Frequenzanalyse Anregungsfrequenzen mit erhöhter Wahrscheinlichkeit den Strömungsvorgang positiv für die Erdölförderung zu beeinflussen. Die vorgeschlagenen Frequenzen erzielten auf verschiedenen Parametern erfolgreich eine positive Beeinflussung des Wasserdurchbruchspunktes, des Entölungsgrades und der relativen Permeabilität. Zur Erhöhung der Aussagekraft der Daten wurden Verfahren der multivariaten Statistik erfolgreich eingesetzt. Zudem wurden positive Rückkopplungseffekte mit dem Einsatz oberflächenaktiver Substanzen nachgewiesen. In einem abschließenden Schritt konnte die Wirkung des Verfahrens zudem durch Kombination mehrere Frequenzen optimiert werden. Diese von hoher Wichtigkeit geprägten Charakteristika zeigen klar das Potential des Verfahrens zum Einsatz als Verfahren der verbesserten Erdölförderung (EOR) auf.:1. Kurzfassung 5 2. Einleitung 6 2.1. Die primäre und sekundäre Förderphase 7 2.2. Tertiäre Fördermethoden 9 2.3. Akustische Verfahren 14 2.4. Aufgabenstellung 17 3. Grundlagen 18 3.1. Projektvorstellung 19 3.1.1. Vorstellung der Sonde 20 3.1.2. Eingrenzung der Laborparameter 22 3.2. Einordnung des Verfahrens in den Stand der Technik 23 3.2.1. Impuls- und Frequenzverfahren 23 3.2.2. Frequenzbereiche 25 3.3. Auswertemethoden 27 3.3.1. Frequenzanalysen 27 3.3.2. Flutversuche und relative Permeabilität 28 3.3.3. Imbibitionsversuche 32 3.4. Grundlagen der mathematischen Methoden 33 3.4.1. Fouriertransformation 34 3.4.2. Gradientenverfahren 34 3.4.3. Regressionsanalyse 37 4. Laborarbeiten 39 4.1. Versuchsaufbau 39 4.1.1. Flutanlage 39 4.1.2. Imbibitionsgefäße 42 4.2. Versuchsdurchführung 44 4.3. Der Versuchsplan der Flutexperimente 48 4.4. Voruntersuchungen 49 4.4.1. Gesteinsproben 49 4.4.2. Fluidproben 50 5. Datenauswertung 52 5.1. Frequenzanalyse 52 5.2. Flutversuche 55 5.2.1. Ergebnis der Regressionsanalyse 59 5.3. Imbibitionsversuche 61 5.4. Phänomenologische Untersuchungen 63 5.4.1. Injektivitätsveränderung 63 5.4.2. Instabile Emulsionsbildung 65 5.5. Weitergehende Forschungsansätze 67 5.5.1. Rückkopplungseffekte mit Tensiden 67 5.5.2. Bohrlochregeneration 69 6. Diskussion 71 7. Zusammenfassung 75

The purpose of this work was to study polymer degradation mechanisms as well as ways to mitigate it. In the area of chemical stability, defined as divalent cation tolerance of acrylic polymers as hydrolysis increases, use of the n-vinyl pyrrolidone (NVP) monomer helps to preserve viscosity and tolerate higher calcium concentrations over those polymers without NVP. Also, ethylenediaminetetraacetate tetrasodium salt (EDTA-Na+4) is shown to sequester calcium ions at alkaline conditions (pH>10) and, in the case of lab-aged post-hydrolyzed poly(AM-co-AMPS), helps to retain full viscosity at all calcium concentrations when EDTA is present at a stoichiometric equivalence of calcium. Many discrepancies exist in the literature concerning the presence or absence of degradation under various field or laboratory conditions. Carbonate and bicarbonate, which are typically present in natural waters but often neglected in lab-prepared brines, prove to be a hidden variable in resolving why Shupe (1981) saw no loss in viscosity when sodium dithionite was added to polymer in the presence of oxygen (with bicarbonates) but others (Knight, 1973 and Levitt and Pope, 2008) observed severe degradation under similar conditions (but without bicarbonates). A commercial HPAM polymer (Flopaam 3630S) has been shown to be stable in the presence of ferrous iron in the absence of oxygen, clarifying an apparent discrepancy in the literature between the results of Yang and Treiber (1985) and Kheradmand (1987). Dissolved oxygen (DO) levels, and not redox potential (ORP) measurements, are often reported in polymer stability research on oxidative degradation. ORP is shown to be a better measure of the onset of degradation because oxygen is initially being consumed and may not appear until substantial degradation has occurred. Although generally believed to be a detriment to polymer stability in the field, aeration of iron-laden source water prior to hydration of polymer may be beneficial in certain cases where exposure to air in unavoidable. Also, a novel process of safely producing sodium dithionite in the field proves to perform better in terms of long-term polymer stability in anaerobic conditions than the traditional method of using a solution made from powder dithionite. Finally, a pre-sheared 5 million Dalton HPAM is successfully injected into a 3 mD carbonate reservoir core plug. Remarkably, permeability reduction factors remain at values close to unity. However, pressure data from ASP tertiary corefloods suggest that polymer is not feasible for field injections. / text

Canada and Venezuela contain massive unconventional oil deposits accounting for over two thirds of newly discovered proven oil reserves since 2002. Canada, primarily in northern Alberta province, has between 1.75 and 1.84 trillion barrels of hydrocarbon resources that as of 2013 are obtained approximately equally through surface extraction or enhanced oil recovery (EOR) (World Energy Council, 2010). Due to their depth and viscosity, thermal based EOR will increasingly be responsible for producing the vast quantities of bitumen residing in Canada’s Athabasca, Cold Lake, and Peace River formations. Although the internationally accepted 174-180 billion barrels recoverable ranks Canada third globally in oil reserves, it represents only a 9-10% average recovery factor of its very high viscosity deposits (World Energy Council, 2010). As thermal techniques are refined and improved, in conjunction with methods under development and integrating elements of existing but currently separate processes, engineers and geoscientists aim to improve recovery rates and add tens of billions of barrels of oil to Canada’s reserves (Cenovus Energy, 2013). The Government of Canada estimates 315 billion barrels recoverable with the right combination of technological improvements and sustained high oil prices (Government of Canada, 2013). Much uncertainty and skepticism surrounds how this 75% increase is to be accomplished. This document entails a thorough analysis of standard and advanced EOR techniques and their potential incremental impact in Canada’s bitumen deposits. Due to the extraordinary volume of hydrocarbon resources in Canada, a small percentage growth in ultimate recovery satisfies years of increased petroleum demand from the developing world, affects the geopolitics within North America and between it and the rest of the world, and provides material benefits to project economics. This paper details the enhanced oil recovery methods used in the oil sands deposits while exploring new developments and their potential technical and economic effect. CMG Stars reservoir simulation is leveraged to test both the feasible recoveries of and validate the physics behind select advanced techniques. These technological and operational improvements are aggregated and an assessment produced on Canada’s total recoverable petroleum reserves. Canada has, by far, the largest bitumen recovery operation in the world (World Energy Council, 2010). Due to its resource base and political environment, the nation is likely to continue as the focus point for new developments in thermal EOR. Reservoir characteristics and project analysis are thus framed using Canada and its reserves. / text

A numerical reservoir model was created to optimize CO₂ Huff-and-Puff operations in the Bakken Shale. Huff-and-Puff is an enhanced oil recovery treatment in which a well alternates between injection, soaking, and production. Injecting CO₂ into the formation and allowing it to “soak” re-pressurizes the reservoir and improves oil mobility, boosting production from the well. A compositional reservoir simulator was used to study the various design components of the Huff-and-Puff process in order to identify the parameters with the largest impact on recovery and understand the reservoir’s response to cyclical CO₂ injection. It was found that starting Huff-and-Puff too early in the life of the well diminishes its effectiveness, and that shorter soaking periods are preferable over longer waiting times. Huff-and-Puff works best in reservoirs with highly-conductive natural fracture networks, which allow CO₂ to migrate deep into the formation and mix with the reservoir fluids. The discretization of the computational domain has a large impact on the simulation results, with coarser gridding corresponding to larger projected recoveries. Doubling the number of hydraulic fractures per stage results in considerably greater CO₂ injection requirements without proportionally larger incremental recovery factors. Incremental recovery from CO₂ Huff-and-Puff appears to be insufficient to make the process commercially feasible under current economic conditions. However, re-injecting mixtures of CO₂ and produced hydrocarbon gases was proven to be technically and economically viable, which could significantly improve profit margins of Huff-and-Puff operations. A substantial portion of this project involved studying alternative numerical methods for modeling hydraulically-fractured reservoir models. A domain decomposition technique known as mortar coupling was used to model the reservoir system as two individually-solved subdomains: fracture and matrix. A mortar-based numerical reservoir simulator was developed and its results compared to a tradition full-domain finite difference model for the Cinco-Ley et al. (1978) finite-conductivity vertical fracture problem. Despite some numerical issues, mortar coupling closely matched Cinco-Ley et al.'s (1978) solution and has potential applications in complex problems where decoupling the fracture-matrix system might be advantageous. / text

En utilisant des approches moléculaires variées, nous avons montré que le gène gpx5 possède au moins trois transcrits dans l'épididyme de souris adulte. A coté d'un messager long codant pour la protéine GPX5 mature, existent en effet deux transcrits tronqués. Les variants de la protéine GPx5, qui correspondent à ces transcrits courts, subissent dans l'épididyme de souris, une maturation post-transcriptionnelle qui repose essentiellement sur des processus de O-glycosylation. Ce travail a aussi permis de préciser que l'expression du gène gpx5 dépasse le territoire épididymaire puisque les transcrits gpx5 peuvent détectés à des niveaux faibles dans d'autres tissus de la sphère génitale chez la souris adulte. C'est le cas par exemple au niveau du testicule ou de la prostate. L'obtention, par des gestations datées, d'embryons de souris à différents stades, a permis de mettre en évidence une expression du gène gpx5 pendant les phases précoces du développement embryonnaire. Cette expression embryonnaire de gpx5 concerne un quatrième variant dont la séquence 3' UTR n'a pu être précisée. Des analyses immunohistochimiques complémentaires sont nécessaires pour confirmer la détection de la protéine GPx5 dans l'embryon précoce de souris et sa localisation dans l'endoderme pariétal.