The Effect of Silica Gel Nanopores and Surfactants on Co2 Hydrate Formation Kinetics: An Experimental and Modeling Study Based on Shrinking Core Model

The carbon dioxide (CO2) hydrate formation kinetics in silica gel (SG) nanopores with the addition of surfactants are studied both experimentally and numerically. SGs with pore sizes of 50 and 100 nm are used as frameworks for hydrate formation in pores. Sodium dodecyl sulfate (SDS) or dodecyltrimethylammonium chloride (DTAC) are used as kinetics promoters which can greatly enhance gas–water mass transfer. An advanced shrinking core model considering CO2 solubility, pore size, surfactants, and capillary effect is established. The results reveal that the reaction rate constant is increased in large pores or in the presence of surfactants, saving up to 49.3 % time to achieve the same amount of gas uptake in 100-nm SG with 500-ppm SDS. The effective diffusion coefficient controlled by a reduction factor drops dramatically due to the enlargement of the reduction factor in small pores and more surfactants, thus hindering the gas diffusion through the formed hydrate shell. The initial water consumed by capillary effect is more prominent in smaller pores and with the addition of surfactants. The initial proportion of water consumed by capillary effect to the total water consumption is only 1%–26.6% without surfactants, but can be up to 74.9% in 50-nm SGs with 500-ppm SDS. This proportion is overall higher in SDS systems than that in studied DTAC systems, but it is not obviously affected by surfactant concentrations. The higher proportion of water consumed by capillaries is speculated to be due to the more capillary tubes with larger radii formed initially in the presence of surfactants. The modeling strategies in this work can be applied to hydrate formation mechanisms in other porous materials.