Molecular Dynamics Simulations to Study the Effect of Fracturing on the Efficiency Of CH4-CO2 Replacement in Hydrates

Feasible techniques for long-term methane production from naturally occurring gas hydrates are being explored in both marine and permafrost geological formations around the world. Most of the deposits are found in low-permeability reservoirs and the economic and efficient exploitation of these is an important issue. One of the techniques gaining momentum in recent years is the replacement of CH4 -hydrates with CO2 -hydrates. Studies have been performed, at both laboratory and field based experimental and simulation scale, to evaluate the feasibility of the in situ mass transfer by injecting CO2 in gaseous, liquid, supercritical and emulsion form. Although thermodynamically feasible, these processes are limited by reaction kinetics and diffusive transport mechanisms. Increasing the permeability and the available surface area can lead to increased heat, mass and pressure transfer across the reservoir. Fracturing technology has been perfected over the years to provide a solution in such low-permeability reservoirs for surface-dependent processes. This work attempts to understand the effects of fracturing technology on the efficiency of this CH4-CO2 replacement process. Simulations are performed at the molecular scale to understand the effect of temperature, initial CO2 concentration and initial surface area on the amount of CH4 hydrates dissociated. A fully saturated methane hydrate lattice is subjected to a uniaxial tensile loading to validate the elastic mechanical properties and create a fracture opening for CO2 injection. The Isothermal Young’s modulus was found to be very close to literature values and equal to 8.25 GPa at 270 K. Liquid CO2 molecules were then injected into an artificial fracture cavity, of known surface area, and the system was equilibrated to reach conditions suitable for CH4 hydrate dissociation and CO2 hydrate formation. The author finds that as the simulation progresses, CH4 molecules are released into the cavity and the presence of CO2 molecules aids in the rapid formation of CH4 nanobubbles. These nanobubbles formed in the vicinity of the hydrate/liquid interface and not near the mouth of the cavity. The CO2 molecules were observed to diffuse into the liquid region and were not a part of the i nanobubble. Dissolved gas and water molecules are found to accumulate near the mouth of the cavity in all cases, potentially leading to secondary hydrate formation at longer time scales. Temperatures studied in this work did not have a significant effect on the replacement process. Simulations with varying initial CO2 concentration, keeping the fracture surface area constant, show that the number of methane molecules released is directly proportional to the initial CO2 concentration. It was also seen that the number of methane molecules released increases with the increase in the initial surface area available for mass transfer. On comparing the positive effect of the two parameters, the initial CO2 concentration proved to have greater positive impact on the number of methane molecules released as compared to the surface area. These results provide some insight into the mechanism of combining the two recovery techniques. They lay the groundwork for further work exploring the use of fracturing as a primary kick-off technique prior to CO2 injection for methane production from hydrates.