Kinetics of CO2 hydrate formation in clayey sand sediments: Implications for CO2 sequestration

Hydrate-based CO₂ sequestration beneath oceanic sediments is an emerging technique that involves the injection of CO₂ into the hydrate stability zone (HSZ) beneath the seabed, forming hydrate cap that structurally traps the injected CO₂ and reduces the risk of leaking CO₂ from the storage sediment. Gas hydrates are adequately stable in sand sediments saturated with fresh water; however, the salinity of oceanic water impairs hydrate formation kinetics, stability, and CO₂ storage capacity. In addition to sandstones, marine sediments are composed of many clay minerals that could affect hydrate formation. Therefore, this study experimentally simulates CO₂ injection into sand and clayey sand sediments to assess the potential of CO₂ hydrate formation. CO₂ hydrates are formed inside a high-pressure reactor, which contains unconsolidated sediment bed/pack (silica sand; mixed sand with bentonite clay: 5 wt% and 10 wt%), saturated with de-ionized water or brine (3.3 wt% NaCl). Hydrate formation experiments were performed at 4 MPa pressure and 274.15 K temperature. Results show that CO₂ hydrate formed within the sand sediment, with induction times of 6 and 8.5 h, for the de-ionized and brine systems, respectively. CO₂ gas mole uptake in the de-ionized system was 71.54 mmol/mol however, in the brine system the gas uptake was 56.95 mmol/mol. Hence this 20.4% reduction in the gas uptake indicated the inhibition effect of salinity. In contrast, in the brine-saturated 5 wt% clay-sand sediment, the induction time was 6.5 h, indicating the promoting effect of the nano-sized clay particles. However, the gas uptake in this brine-saturated clay-sand sediment was reduced by 45.51% compared to the brine-saturated sand sediment. Increasing the clay content to 10 wt% prevented CO₂ hydrate formation due to porosity reduction. Moreover, de-ionized water in clayey sand sediments prevented hydrate formation due to clay swelling. Finally, CO₂ hydrate formation at the end of each experiment was visually confirmed.