PVTx measurements of mixed clathrate hydrates in batch conditions under different crystallization rates: Influence on equilibrium

Saheb Maghsoodloo Babakhani (1, 2, 3) , Baptiste Bouillot (1, 2, 3) , Jérôme Douzet (1, 2, 3) , Son Ho-Van (1, 2, 3) , Jean-Michel Herri (2, 1, 3)

1 PEG-ENSMSE - Département Procédés pour l'Environnement et Géoressources
2 SPIN-ENSMSE - Centre Sciences des Processus Industriels et Naturels
3 LGF-ENSMSE - Laboratoire Georges Friedel

Notwithstanding the numerous studies about classical temperature and pressure equilibrium of mixed gas hydrates, few provide hydrate composition and volume at local and final equilibrium under batch conditions. Therefore, required new phase equilibrium data for mixed gas hydrates including CO₂-C₃H₈, C₂H₆-nC₄H₁₀, CH₄-nC₄H₁₀, CO₂-C₂H₆-C₃H₈, CH₄-C₂H₆-nC₄H₁₀ and CH₄-C₂H₆ -C₃H₈-nC₄H₁₀ are presented in this paper. Moreover, results contain hydrate phase properties such as hydrate volume and density, storage capacity, water conversion and guest composition in all phases (et al., liquid and hydrate). Importantly, effect of crystallization rate on final state has been evaluated. Finally the experimental results were compared to the thermodynamic model of van der Waals and Platteeuw to investigate kinetic effects. Experimental results show that equilibrium pressures at final state are dissimilar with respect to the crystallization rate. Furthermore, the hydrate volume formed at slow crystallization rate is noticeably lower than at quick. Noticeably, storage capacity in the case of slow crystallization is higher which could be crucial for industry. Also, the guest composition in hydrate phase at final state differs. Enclathration of heavier molecules is more significant at slow crystallization rate, and the hydrate phase seems to be more homogeneous according to the thermodynamic study. Indeed, modelling results, that assume the hydrate phase to be homogeneous in composition, show better agreement with the slow crystallization results for both equilibrium pressure and guest distribution in hydrate phase. This elucidates that, at quick crystallization rate, thermodynamic equilibrium cannot be reached. In conclusion, how kinetics influence the design of clathrate hydrate based industrial applications such as energy storage and transportation, carbon capture sequestration etc. are demonstrated.

Mots clés: thermodynamics; crystallization; non- equilibrium; modeling; Non-equilibrium; Modelling; clathrate hydrates; phase equilibria

Domaines: Génie des procédés; Chimie théorique et/ou physique

Saheb Maghsoodloo Babakhani, Baptiste Bouillot, Jérôme Douzet, Son Ho-Van, Jean-Michel Herri. PVTx measurements of mixed clathrate hydrates in batch conditions under different crystallization rates: Influence on equilibrium. Journal of Chemical Thermodynamics, 2018, 122, pp.73-84. ⟨10.1016/j.jct.2018.03.006⟩. ⟨hal-01738236⟩