Demystifying Wettability Alteration in Kerogen as a Function of its Geochemistry and Reservoir Temperature and Pressure Using Molecular Dynamics Simulations

Development of reliable models for hydrocarbon-in-place and water saturation estimation requires knowledge about wettability of mudrocks and the parameters (including rock properties and reservoir condition) affecting it. A significant volume fraction of organic-rich mudrocks is composed of kerogen. Therefore, wettability of kerogen affects the overall wettability of organic-rich mudrocks. The chemical composition and structure of kerogen varies with kerogen type and thermal maturity, which affects the surface properties of kerogen such as wettability. In a recent publication, we demonstrated using experimental techniques that kerogen could be water-wet at low thermal maturities and oil-wet at higher thermal maturities. However, the impacts of kerogen type and reservoir temperature/pressure conditions on kerogen and mudrock wettability is yet to be quantified. Therefore, the objectives of this paper include (i) quantifying the impacts of kerogen molecular structure and composition on water adsorption capacities, (ii) quantifying the impacts of reservoir pressure and temperature on water adsorption capacity of kerogen using molecular dynamics (MD) simulations. In order to achieve the aforementioned objectives, we use a combination of molecular dynamics simulations and experimental work. The inputs to the molecular dynamics simulations include realistic models of kerogen, which are condensed to porous kerogen structures. Water molecules are filled in kerogen pore structure and MD simulation is performed. The outputs of the simulations include radial distribution function (RDF), and adsorption isotherms of water on kerogen for different kerogen types, thermal maturities, and temperature conditions. The adsorption processes are modelled for pressure and temperature conditions ranging from 0 to 35 MPa and 320 to 370 K, respectively. The outcomes of molecular dynamics simulations demonstrated that the water adsorption capacities of kerogen vary significantly with kerogen type, thermal maturity, and temperature and pressure conditions. The RDF results showed that the water adsorption capacity decreased from type I to type III kerogen. The water adsorption capacity of kerogen was found to increase by 128% with 38% increase in oxygen content. The increase in the adsorption capacity was attributed to the strong attraction between oxygen containing functional groups in kerogen and water. The adsorption isotherms of water and kerogen samples showed that the water adsorption capacity decreased by 0.19 mmol/g as the temperature increased from 320 K to 370 K. The average water adsorption capacity of kerogen was found to increase by 20% with increase in pressure by 34 MPa. The results obtained from molecular dynamics simulations were found to be in good agreement with experimental results. The results of this paper can be used to predict the adsorption capacities of any kerogen with the availability of geochemical information. This important property of kerogen is required for estimating kerogen wettability and can enhance understanding of fluid-flow mechanisms in organic-rich mudrocks.