Sequential Formation of CO 2 Hydrates in a Confined Environment: Description of Phase Equilibrium Boundary, Gas Consumption, Formation Rate and Memory Effect

Since 1980, one of the most promising solutions for the exploitation of natural gas hydrate reservoirs was found to be the replacement of methane with carbon dioxide in order to improve the efficiency of methane recovery and, at the same time, permanently store carbon dioxide. However, the process efficiency is still too low and far from reaching technical maturity and becoming economically competitive. In this sense, studying the intrinsic properties of CO 2 hydrates formation and dissociation processes may help in better defining the reasons for this low efficiency and finding feasible solutions. This work deals with carbon dioxide hydrates formation in a natural silica-based porous medium and in fresh water. A lab-scale apparatus was used for experiments, which were carried out consecutively and with the same gas–water mixture in order to detect the possible occurrence of the “memory effect”. Six tests were carried out: the quantity of gas available for the formation of hydrates led to an initial pressure equal to 39.4 bar within the reactor (the initial pressure was 46 bar; however, the dissolution of CO 2 in water during the first test caused a reduction in the quantity of gas available for the process). Each experiment started and ended at temperatures equal or higher than 20 °C. Considering the local pressures, these temperatures ensured the complete dissociation of hydrates. Besides thermodynamic parameters, the gas consumption and the rate constant were evaluated throughout the whole of the experiments. Conversely to what is asserted in the literature, the results demonstrated the weak persistence of the memory effect at a temperature slightly above 25 °C. As expected, ice formation competed with hydrates; however, during tests, it caused the partial release of carbon dioxide previously trapped into hydrates or dissolved in water. Finally, the rate constant completely agreed with the labile Cluster Theory and proved that primordial clusters and hydrate crystals formed and dissociated during the whole test. The first phenomenon was predominant during the formation phase, while the opposite occurred during the following step. The rate constant was found to be an effective parameter to quantify differences between measured and real equilibrium conditions for the system.