HOW THE LOWERING OF PRESSURE OR THE FORMATION OF ICE AFFECT THE FORMATION AND DISSOCIATION OF METHANE HYDRATES: VARIATIONS IN TERMS OF METASTABLE PHASE AND ANOMALOUS SELF-PRESERVATION

This research proposes the multiple and consecutive formation of methane hydrates with the same gas–water mixture and in a small-scale reactor. The scope consisted of better exploring how the variation of the initial pressure of the system modified the formation and dissociation processes. One of the most promising solutions for gas hydrates exploitation consists in the replacement of methane with carbon dioxide. This process inevitably requires the formation of CO2 hydrates; thus, more details and analyses on the driving forces of the formation process are required in order to improve the overall replacement efficiency. Also, the competition with ice was analyzed. Nine tests were carried out in order to consider all these parameters. Each test was characterized thermodynamically and the time required to complete each specific phase of the process was measured. The tests were carried out at two different initial pressures: 60 and 50 bar, respectively. It was found that the main effect, associated with a lower initial pressure and/or with the presence of ice, is the stretching of the so-called metastable phase; since the local conditions became suitable for the formation of hydrates, the system required more time to begin in these latter cases. In the tests made at 60 bar, the delay in hydrate formation related to the metastable phase was equal to 0.73–1.04 h, while it ranged from 7.29 to 15.16 h in the tests made at 50 bar. Moreover, the results proved that the presence of ice hindered the formation process by reducing the heat transfer rate and by lowering the volume available for the process. Conversely, the begin of the dissociation phase was similar in all the experiments: the anomalous self-preservation, or the capability of the system to preserve itself even outside the hydrate stability zone was not observed, proving again that these limiting factors (lower initial pressure and ice formation) mainly affected the process during the formation phase.