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Poster De Conférence Année : 2019

Thermodynamics of cyclopentane hydrates formation from brine: experimental and modelling study

Résumé

Cyclopentane hydrates-based salt-removal has been considered to be one promising technologies for desalination because it requires a low amount of operating compared to traditional methods such as thermal distillation, membrane separation, or freezing. In order to design a desalination, or water treatment, plant, it is necessary to understand both the thermodynamics of crystallization of hydrates (CPH) in presence of salt, and the kinetics. Therefore, this study aims to determine and model the equilibria of cyclopentane hydrates in the presence of electrolytes. Eight salt mixtures have been considered: NaCl, KCl, NaCl-KCl, CaCl2, Na2SO4, MgCl2, MgCl2-NaCl, MgCl2-NaCl-KCl, with a wide range of concentrations. Two successive experimental procedures, quick and slow, have been applied to determine equilibrium temperatures. The objective of the quick procedure is to provide an initial estimate of the equilibrium temperature. Then, the slow procedure is used to obtain more accurate data. Experimental results show that equilibrium temperatures dropped significantly with an increase in salt concentration, whatever the kinds of salt. In comparison with the literature, the final slow procedure in pure water provides, or with NaCl, provide results very close to studies of Kishimoto et al. and Zylyftari et al., obtained either by slow dissociation or micro Differential Scanning Calorimetry (µ-DSC). Moreover, salt co-precipitation can be achieved simultaneously with the cyclopentane hydrate formation. For instance, the eutectic point of four phase equilibrium of {liquid water + liquid CP + CPH + Na2SO4.10H2O} has been obtained in this study. This provides possibility for by-products, or value added products, recovery thanks to CPH. Afterward, four thermodynamic approaches have been considered for the results modelling. One is based on Standard Freezing Point Depression method. Another one considers the very new Hu-Lee-Sum (HLS) correlation, designed to predict the suppression temperature of clathrate hydrates when an additive is introduced into the system. The two last models are based on van der Waals and Platteeuw model, using either Kihara potential, or a correlation instead (ABOC). All models provide data with a difference lower than 0.7°C compared to experimental results. However, the best method is the ABOC method (activity based occupancy correlation). This approach uses a correlation between the clathrate occupancy, and the water activity. It furnishes equilibrium temperatures within 0.2°C uncertainty.
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Dates et versions

hal-02311213 , version 1 (10-10-2019)

Identifiants

  • HAL Id : hal-02311213 , version 1

Citer

Baptiste Bouillot, Son Ho-Van, Jérome Douzet, Ana Cameirao, Daniel Garcia, et al.. Thermodynamics of cyclopentane hydrates formation from brine: experimental and modelling study. JETC 2019 - Joint European Thermodynamics Conference, May 2019, Barcelone, Spain. . ⟨hal-02311213⟩
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