Skip to Main content Skip to Navigation

Hydrate Phase Equilibria Study of CO2 Containing Gases in Thermodynamic Promoter Aqueous Mixtures

Abstract : This thesis addresses the measurement and thermodynamic analysis of the phase equilibrium behavior of carbon dioxide (CO2) hydrate-forming systems in the context of alternative capture engineering approaches. The development of new technologies based on gas hydrates requires specific temperature and pressure conditions and the utilization of thermodynamic promoters that are beyond usual operations and existing databases. Accurate knowledge of gas hydrates formation and dissociation from thermodynamics point of view in the presence of chemical additives is necessary for modeling purposes and to establish the feasibility of emerging industrial processes involving gas hydrates. In this thesis, a new experimental set-up and method for measuring pressure, temperature and compositional phase equilibrium data of high accuracy are presented. The equipment is based on the ‘static-analytic' technique with gas phase capillary sampling and it is suitable for measurements in a wide temperature range (i.e. 233 to 373 K) and pressures up to 60 MPa. New phase equilibrium data in the (CO2 + methane), (CO2 + nitrogen) and (CO2 + hydrogen) systems under hydrate formation conditions were measured following an isochoric pressure-search method in combination with gas phase compositional analysis. The equilibrium data generated in this work are compared with literature data and also with the predictions of two thermodynamic literature models. Comparisons between experimental and predicted hydrate dissociation data suggest a need of readjusting model parameters for CO2 hydrate-forming systems. In addition, the thermodynamic stability of Tetra-n-Butyl Ammonium Bromide (TBAB) semi-clathrates (sc) with pure and mixed gases was investigated. The largest promotion effect (> 90% reduction in hydrate formation pressure) is observed for (TBAB + nitrogen) sc. The experimental results suggest that CO2 can be separated from highly to low concentrated industrial/flue gas mixtures at mild temperatures and low pressures by using TBAB as thermodynamic promoter. The pressure required for hydrate formation from (CO2 + nitrogen) gas mixtures is reduced by 60% in the presence of TBAB.
Document type :
Complete list of metadata

Cited literature [202 references]  Display  Hide  Download
Contributor : ABES STAR :  Contact
Submitted on : Tuesday, July 17, 2012 - 4:25:58 PM
Last modification on : Friday, April 29, 2022 - 11:09:16 AM
Long-term archiving on: : Thursday, October 18, 2012 - 2:50:25 AM


Version validated by the jury (STAR)


  • HAL Id : pastel-00718604, version 1


Veronica Belandria. Hydrate Phase Equilibria Study of CO2 Containing Gases in Thermodynamic Promoter Aqueous Mixtures. Other. Ecole Nationale Supérieure des Mines de Paris, 2012. English. ⟨NNT : 2012ENMP0018⟩. ⟨pastel-00718604⟩



Record views


Files downloads