Small Alcohols as Surfactants and Hydrate Promotors

Many methods to produce hydrate reservoirs have been proposed in the last three decades. Thermal stimulation and injection of thermodynamic hydrate inhibitors are just two examples of methods which have seen reduced attention due to their high cost. However, different methods for producing hydrates are not evaluated thermodynamically prior to planning expensive experiments or pilot tests. This can be due to lack of a thermodynamic toolbox for the purpose. Another challenge is the lack of focus on the limitations of the hydrate phase transition itself. The interface between hydrate and liquid water is a kinetic bottle neck. Reducing pressure does not address this problem. An injection of CO2 will lead to the formation of a new CO2 hydrate. This hydrate formation is an efficient heat source for dissociating hydrate since heating breaks the hydrogen bonds, directly addressing the problem of nano scale kinetic limitation. Adding limited amounts of N2 increases the permeability of the injection gas. The addition of surfactant increases gas/water interface dynamics and promotes heterogeneous hydrate formation. In this work we demonstrate a residual thermodynamic scheme that allows thermodynamic analysis of different routes for hydrate formation and dissociation. We demonstrate that 20 moles per N2 added to the CO2 is thermodynamically feasible for generating a new hydrate into the pores. When N2 is added, the available hydrate formation enthalpy is reduced as compared to pure CO2, but is still considered sufficient. Up to 3 mole percent ethanol in the free pore water is also thermodynamically feasible. The addition of alcohol will not greatly disturb the ability to form new hydrate from the injection gas. Homogeneous hydrate formation from dissolved CH4 and/or CO2 is limited in amount and not important. However, the hydrate stability limits related to concentration of hydrate former in surrounding water are important. Mineral surfaces can act as hydrate promotors through direct adsorption, or adsorption in water that is structured by mineral surface charges. These aspects will be quantified in a follow-up paper, along with kinetic modelling based on thermodynamic modelling in this work.