Effect of main functional groups of cement slurry additives on the stability of methane hydrate: Experiment and molecular dynamics simulation

There are a lot of hydrates in deep-water and shallow layer, which accumulate at relatively shallow depths (<100–120 m). During cementation in the deep-water shallow formation, the free inorganic ions and organic molecules in the cement slurry filtrate enter the formation via percolation, which may affect the stability of the hydrate. The free organic matter in cement slurry acts mainly as retarder, fluid loss additive and dispersant. First, the representative fluid loss additive BXF-200 L, retarder PC-H21L, and dispersant PC-F41L were selected for infrared spectroscopy. Then, the influence of BXF-200 L, which contains all the previously mentioned functional groups, was studied for its impact on hydrate stability using an experimental method. Second, a molecular dynamics simulation method was used to study the adsorption properties of the functional groups on the surface of sI methane hydrate under canonical (NVT) ensemble, which it is the most widely distributed hydrate type in nature. What is more, in order to characterize the influence of functional groups on the decomposition of methane hydrate, the molecular conformation, mean square displacement (MSD), diffusion coefficient (D) and adsorption energy (Eadsorption) were calculated using the dynamics simulation trajectory of sI methane hydrate. The experimental results showed that the main functional groups in cement slurry filtrate additives were carboxyl, sulfonate, and acylamino groups. Further, BXF-200 L can promote hydrate decomposition. Subsequently, the simulation results showed that under the same conditions, the adsorption energy of sulfonate group on the surface of methane hydrate was the largest and the adsorption capacity was the greatest. When the concentration was ≤ 1 mol%, among the three functional groups, acylamino had the most obvious promoting effect on the decomposition of sI methane hydrate, and the hydrate decomposition rate increased by 16.31%. When the concentration was more than 1 mol%, among the three functional groups, acylamino had the most obvious promoting effect on the decomposition of sI methane hydrate, and the hydrate decomposition rate increased by 16.31%. When the concentration was more than 1 mol%, the decomposition rate of hydrate was increased under the interaction of carboxyl, acylamino, and sulfonate groups, by 12.49%, 19.46% and 27.74%, respectively, compared with that under pure water-hydrate system.