Can hydrate form in carbon dioxide from dissolved water?

Abstract

Transport of carbon dioxide in offshore pipelines involves high pressures and low temperatures, which may lead to formation of hydrate from the residual dissolved water and carbon dioxide. While thermodynamics is able to tell us whether the hydrate phase will be stable, the question of whether its formation will actually occur under given pipeline conditions does not have a straightforward answer. In this work, we have made use of water properties obtained from molecular simulations to examine the thermodynamics of hydrate formation from water dissolved in carbon dioxide. This paper proposes a method that allows estimation of absolute thermodynamic properties and thus makes it possible to compare free energy changes due to several possible phase transitions and determine the most probable transition. This information can be used directly to choose the optimum hydrate prevention strategy. We have found that hydrate formation from a carbon dioxide solution will be thermodynamically viable at water concentration exceeding a certain level; a conclusion also supported by several previous studies. We have also extended the quantitative analysis of the thermodynamics and the kinetics of formation through a modified version of phase field theory (PFT). The work presents the way to obtain parameters required for the practical implementation of the PFT in the case of hydrate formation, as well as outlines the estimation of thermodynamic properties for systems unable to reach true equilibrium.