The methane adsorption onto a hydrated surface of hydrophobic silica AM1 alone and impregnated by arginine, and silica gel Si-100 has been studied using low-temperature 1H NMR spectroscopy. It has been shown that the methane adsorption onto the AM1 surface depends on the degree of hydration and pretreatment type. The maximum adsorption (up to 80 mg/g) is observed for a sample hydrated after complete drying. It has been established that the adsorption is determined by a number of clusters of bound water of small radii. Based on a shape of the temperature dependence of the adsorption, it has been assumed that not only physical adsorption occurs, but also the quasi-solid methane hydrates are formed. It has been established that the amount of methane adsorbed onto a surface of a composite system AM1/arginine under isobaric conditions increases by tens of times (from 0.5 to 80 mg/g) in the presence of pre-adsorbed water pre-adsorbed at the surface. Probable mechanisms of the methane adsorption are physical adsorption on a surface, condensation in narrow voids between silica nanoparticles and nano-scaled (1-10 nm) water clusters, and the formation of solid (clathrate) methane hydrates. Water, adsorbed at a surface in a wide range of hydration, forms various clusters. This water is mainly strongly associated and characterized by chemical shifts in the range dH = 4-6 ppm. The hydrate structures with methane/water are quite stable and can exist even in the chloroform medium. However, in this case, a part of water transforms into a weakly associated state and it is observed at dH = 1.5-2 ppm.
Methane Adsorption Behavior and Energy Variations of Brittle Tectonically Deformed Coal under High Temperature and High Pressure
