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Experimental measurement and thermodynamic modelling of phase equilibria of semi-clathrate hydrates of (CO2 + tetra-n-butyl-ammonium bromide) aqueous solution
Institution:1. Faculty of Petroleum Engineering, Petroleum University of Technology (PUT), Ahwaz, Iran;2. Department of Chemical Engineering, Iran University of Science and Technology (IUST), Tehran, Iran;3. Institut de Recherche en Génie Chimique et Pétrolier (IRGCP), Paris Cedex, France;4. Thermodynamics Research Unit, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4041, South Africa;1. Department of Safety Engineering, Heilongjiang University of Science and Technology, Harbin 150022, Heilongjiang, China;2. Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117585, Singapore;3. Key Laboratory of Gas Hydrate, Ministry of Land and Resources, Qingdao Institute of Marine Geology, Qingdao 266071, China;1. Shandong Provincial Key Laboratory of Civil Engineering Disaster Prevention and Mitigation (Shandong University of Science and Technology), Qingdao 266590, China;2. The Key Laboratory of Gas Hydrate, Ministry of Land and Resources, Qingdao 266071, China;1. Center for Energy Resources Engineering, Department of Chemical and Biochemical Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark;2. Mines ParisTech PSL Research Université, CTP-Centre Thermodynamic of Processes, 35 Rue Saint Honoré, 77305 Fontainebleau, France;1. Department of Petroleum Engineering, Petroleum Engineering Petroleum University of Technology (PUT) , P.O. Box 63431, Ahwaz, Iran;2. Department of Gas Engineering, Petroleum Engineering, Petroleum University of Technology (PUT) , P.O. Box 63431, Ahwaz, Iran;3. IOR\\EOR Research Institute, National Iranian Oil Company (NIOC), Tehran, Iran
Abstract:Comprehensive studies on semi-clathrate hydrates phase equilibria are still required to better understand characteristics of this type of clathrates. In this communication, new experimental data on the dissociation conditions of semi-clathrate hydrates of {carbon dioxide + tetra-n-butyl-ammonium bromide (TBAB)} aqueous solution are first reported in a wide range of TBAB concentrations and at different pressures and temperatures. A thermodynamic model is then proposed to predict the dissociation conditions of the semi-clathrate hydrates for the latter system. The (hydrate + TBAB) aqueous solution (H + Lw) phase equilibrium prediction is considered based on Gibbs free energy minimization approach. A modified van der Waals–Platteeuw solid solution theory developed based on the (H + Lw) equilibrium information is employed to predict the dissociation conditions of semi-clathrate hydrates of carbon dioxide + TBAB. The properties of the aqueous solution are estimated using the AMSA-NRTL electrolyte model (considering the association and hydration of ions). The Peng–Robinson equation of state is used for estimating the gas/vapour phase properties. Results show that the proposed model satisfactorily predicts the experimental values with an average absolute relative deviation of approximately 13%.
Keywords:Gas hydrate  Semi-clathrate hydrate  TBAB  Carbon dioxide  Thermodynamic model
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