Thermodynamic assessment and microscale Raman spectroscopy of binary CO2/CH4 hydrates produced during replacement applications in natural reservoirs

The present research deals with the micro – scale characterization of sI hydrates containing a binary mixture of methane and carbon dioxide. The application of replacement strategies in natural hydrate reservoirs, always leads to the formation of “mixed” hydrates, whose mechanical and chemical properties are different from those of pure CH4 and CO2 hydrates. As a function of the technique used for the process and due to the variability of the systems, a wide range of different compositions and morphologies can be obtained and the current literature must be expanded, in order to achieve a wide and accurate experimental database of CO2/CH4 hydrate properties. In this work, binary CO2/CH4 hydrates binary CO2/CH4 hydrates were produced in a small – scale reactor and then supercooled, in order to favour their extraction from the reactor and their stability at environmental conditions for a certain period of time. The gas hydrates, prepared with CO2 hydrates of pure water and with CH4 and CO2 mixtures, also in the presence of specific sands, were ex situ analysed by the use Raman-spectroscopy that confirmed the gas uptake in the hydrate structures by identification of the fingerprint of CH4 and CO2 occupancy in the hydrates. The characteristic of water inside the gas hydrates and the interaction between the host molecules and the lattice of water molecules was clarified. The different gas hydrates, analysed by Field Emission Scanning Electron Microscopy instrument equipped with “Coolstage head” under high vacuum condition, differed in morphology and surface features. The analysis of water Raman spectra of the different GHs permitted to describe the relation between symmetric and asymmetric OHs bands, but also provided information about the characteristics of water inside the different GHs, showing that the least ordered water structure was that of GHs containing sand, while the most ordered one was present on binary CO2/CH4 hydrates.