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Mitigating corrosion risks in oil and gas equipment by electrochemical protection : top of the line corrosionAjayi, Fredric January 2015 (has links)
This study investigated the corrosion processes at the top and bottom of carbon steel pipelines transporting wet gases, and studied possible chemical mitigation strategies. First, immersion tests were carried out using carbon steel to study the effects of de-aeration with high purity nitrogen gas on the corrosion rate. Secondly, the corrosion rate was assessed for varying chloride ion concentrations in an aerated environment. In general, increasing de-aeration time changes the corrosion mechanism from mass transfer oxygen reduction to water reduction reaction. However, oxygen solubility controlled the corrosion process in aerated solution containing different chloride ion concentrations. A special two-electrode cell was designed for the top of the line corrosion (TLC) electrochemical measurements but a conventional three electrode cell was used for the bottom of the line corrosion (BLC) measurements. The TLC rate increases with temperature, and X-Ray Diffraction (XRD) confirmed the presence of chukanovite {Fe2(CO3)(OH)2}and possibly ferrous carbonate corrosion products at 40oC and 60oC respectively. However, for the BLC, the cementite phase remained on the metal surface after preferential dissolution of the ferrite phase in the carbon steel. Addition of acetic acid (HAc) locally dissolved the initially FeCO3 film formed on the metal surface, causing local corrosion damage. Addition of methyl di ethanol amine (MDEA) as a pH stabiliser reduced TLC and BLC rates due to enhanced stability of FeCO3 at pH 5.7-6.3. When Zn2+ ions were added as ZnCl2, both Fe2O3 and ZnCO3 were formed at reduced corrosion rate. Whenever FeCO3 film was damaged/dissolved by HAc addition of neither pH stabiliser; MDEA nor hydrate preventer; mono ethylene glycol (MEG) could not re-establish a protective film on the metal surface. The following organic inhibitors were investigated as potential mitigators of TLC: 2-mercaptobenzimidazole (2MBI), 2-amino-5-ethyl-1,3,4-thiodiazole (AETDA), 2-phenyl-2-imidazoline (2PI), dicyclohexylamine (DHA), and a commercial inhibitor formulation (CI-A). The inhibition efficiency (IE%) was found to increase in the order CI-A > 2MBI > AETDA > DHA. Their efficiency increases (except DHA) with inhibitor concentrations both at top and bottom of the line. 2MBI and CI-A behaved as mixed inhibitors but AETDA behaved as cathodic inhibitor, all were best fitted to a simple Langmuir adsorption isotherm. However, IE% of DHA decreased at higher inhibitor concentrations. Surprisingly, 2PI inhibitor increased the corrosion rate, and the corrosion rate further increased with increase inhibitor concentrations. Weight loss measurements results of TLC are also presented which showed lower inhibition efficiency for all the inhibitors investigated compared with electrochemical measurements in similar environments. The free energy of adsorption (∆Goads values for 2MBI and AETDA are around -36kJ.mol-1 while for CI-A the value was -15kJ.mol-1 (-7kJ.mol-1 in the presence of HAc). This is evidence for adsorption of 2MBI and AETDA on the metal surface by chemisorption with CI-A by physisorption. XPS analysis confirmed the presence of FeCO3 and FeOOH as corrosion products in the brine solution in the absence and presence of HAc containing different corrosion inhibitors.
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Influence de l'humidité de l'air sur la perte de charge d'un dépôt nanostructuré / Influence of moisture on the pressure drop of nanostructured depositRibeyre, Quentin 09 June 2015 (has links)
Dans l’industrie, des systèmes de protection collectifs doivent être mis en œuvre pour protéger aussi bien les travailleurs que l’environnement. Des filtres à fibres sont généralement disposés dans les circuits de ventilation générale pour capter ces particules en suspension dans l’air. Les performances de ces media fibreux en termes d’efficacité de collecte et consommation énergétique sont relativement bien documentées lors de leur fonctionnement dans des conditions standards (humidité et température ambiantes). Cependant, peu d’études s’intéressent à l’interaction de l’humidité de l’air avec un dépôt composé de particules nanostructurées collectées par ces media filtrants et son incidence sur l’évolution de la perte de charge. Le travail de thèse a donc consisté dans un premier temps à la mesure d’isothermes de sorption de quatre poudres nanostructurées. Un modèle semi-prédictif d’adsorption-condensation basé sur le modèle GAB et la loi de Kelvin a ensuite été proposé. La seconde partie de l’étude a permis de décrire expérimentalement la variation de perte de charge et d’épaisseur d’un milieu poreux, formé par ces mêmes particules nanostructurées, pour différentes valeurs d’humidité. Grâce à la variation d’épaisseur du milieu déterminée par trigonométrie laser et au modèle d’adsorption-condensation, la porosité pour chaque valeur d’humidité relative a pu être calculée. En incorporant les valeurs de porosité et d’épaisseur dans trois modèles de perte de charge, il a été possible de représenter de façon satisfaisante les résultats expérimentaux. Enfin, une analyse rhéologique des poudres est proposée pour quantifier leur augmentation de cohésion sous humidité / Air quality has emerged as a major public environmental and health issue. Almost all fine particles in the air are man-made or manufactured and there are many questions regarding the impact of ultrafine (<100nm) particles on human health. Thus, in most cases, institutions use large-scale protection equipment to protect workers. These institutions often use particulate air filters placed within the flow of general ventilation. Almost all of the available data corresponds to standard ambient air conditions. Despite this, few studies focus on the interaction of water moisture on the deposit formed by these accumulated nanoparticles and the impact on the pressure drop. The first part of this study consists of the measurement of sorption isotherms of four nanostructured powders. A semi-predictive sorption model based on the theory of the multimolecular adsorption (described by the GAB equation) and on the capillary condensation (Kelvin’s law) was developed. The second part of the study experimentally describes the thickness and pressure drop variation of a porous medium formed by these nanostructured particles for different values of humidity. Through the thickness variation of the media - determined by laser trigonometry - and adsorption-condensation model, the porosity for each humidity value has been calculated. Following this, three pressure drop models available in the literature have been modified by introducing cake thickness and porosity variation according to relative humidity. This allows us to model the experimental data for all the samples. Finally, a rheological analysis of powders is proposed to quantify the cohesion changes under moisture conditions
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