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Cristallisation non-stoechiométrique et modélisation d’un flash thermodynamique : Cas des hydrates mixtes de gaz

Abstract : Clathrate Hydrates are ice-like compounds that can be formed under high pressure and low temperature. They are composed of water and small molecules of ‘’gas’’. Hence they are usually called gas hydrates. They are involved in a significant issue of the oil industry, the hydrate plugs in pipelines (flow-assurance), as well as gas capture and storage, air conditioning… Moreover, methane hydrates can be found in sediments in deep sea and permafrost. That is why they are also considered as a significant methane resource on earth. Since they are non-stoichiometric compounds, it is difficult to model these crystals in process simulation. Furthermore, the speed of crystallization seems to influence the hydrate composition. Therefore, a modeling of the hydrate crystallization taking into account the history of the solid formation could be an interesting tool. In this work, a successive thermodynamic flash approach is presented according to two different hypotheses: heterogeneous hydrate phase during the crystal growth, and homogeneous hydrate phase. The main idea of these procedures is to discretize the crystal growth while the hydrate volume is increasing. Hence, three phase flash calculations are performed on the system. Each time, the previous amount of hydrate that has been formed is removed (at each iteration). The results of such algorithms are compared to batch experiments at low and quick crystallization rates (Duyen et al. 2016). The flash algorithms at given temperature (only one degree of freedom) give accurate results. The predicted final pressure and the hydrate volume are calculated within 7% accuracy. Moreover, the flash calculation results with no hydrate reorganization are closer to experiments at quick crystallization rate, whereas the experiment at low crystallization rate is better predicted with the second hypothesis (reorganization of the hydrate phase during growth). This work and its results provide a more realistic and comprehensive view of gas hydrate crystallization (more details in Bouillot and Herri, 2016).
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B Bouillot Cristal 8 2016.pdf
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  • HAL Id : hal-01327031, version 1


Baptiste Bouillot, Jean-Michel Herri. Cristallisation non-stoechiométrique et modélisation d’un flash thermodynamique : Cas des hydrates mixtes de gaz. Cristal Rouen 2016 - 8 ème édition du colloque Cristallisation et Précipitation Industrielles, L'équipe Cristallogénèse du Laboratoire de Sciences et Méthodes Séparatives (SMS) - Université de Rouen; Université de Rouen May 2016, Mont-Saint-Aignan, France. pp.13-1 à 13-8. ⟨hal-01327031⟩



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