Experimental and thermodynamic modelling of hydrate dissociation conditions for CO2 + propane mixtures

The possibility of hydrate formation poses a central issue for Carbon Capture and Storage (CCS) and Enhanced Oil Recovery with Water-Alternating-Gas (EOR/WAG) injection projects. In most of the cases, however, the available fluid for this purpose consists of a CO2-rich stream containing contaminants such as hydrocarbons and permanent gases. As a result, there is a growing interest in evaluating the effect of small impurities concentrations on the phase behaviour of such streams. This work investigates the impact of propane as a promoter in carbon dioxide hydrate formation, covering a concentration range in the feed gas phase between 10 and 69% on mole basis. The study also considers the L-w-L-CO2-H region, taking into account liquid and supercritical transportation commonly encountered in CCS projects. Additionally, a procedure to estimate uncertainties in the graphical determination of the dissociation temperature and pressure is discussed. The thermodynamic modelling approach includes three different modifications of cubic equations of state (CEoS): asymmetric mixing rule, advanced Huron-Vidal mixing rule, and cubic-plus-association approach. An alternative procedure based on setting different sets of CO2 Kihara's parameters when shifting between structures was also used. While satisfactory average temperature deviations were obtained for those equations of state, maximum deviation between calculated and experimental temperatures spanned from 0.5 to 2.5 K, depending on the thermodynamic model.