Development of Carbon Sequestration Options by Studying Carbon Dioxide-Methane Exchange in Hydrates

Gas hydrates form naturally at high pressures (>4 MPa) and low temperatures (<4 oC) when a set number of water molecules form a cage in which small gas molecules can be entrapped as guests. It is estimated that about 700,000 trillion cubic feet (tcf) of methane (CH4) exist naturally as hydrates in marine and permafrost environments, which is more than any other natural sources combined as CH4 hydrates contain about 14 wt% CH4. However, a vast amount of gas hydrates exist in marine environments, which makes gas extraction an environmental challenge, both for potential gas losses during extraction and the potential impact of CH4 extraction on seafloor stability. From the climate change point of view, a 100 ppm increase in atmospheric carbon dioxide (CO2) levels over the past century is of urgent concern. A potential solution to both of these issues is to simultaneously exchange CH4 with CO2 in natural hydrate reserves by forming more stable CO2 hydrates. This approach would minimize disturbances to the host sediment matrix of the seafloor while sequestering CO2. Understanding hydrate growth over time is imperative to prepare for large scale CH4 extraction coupled with CO2 sequestration. In this study, we performed macroscale experiments in a 200 mL high-pressure Jerguson cell that mimicked the pressure-temperature conditions of the seafloor. A total of 13 runs were performed under varying conditions. These included the formation of CH4 hydrates, followed by a CO2 gas injection and CO2 hydrate formation followed by a CH4 gas injection. Results demonstrated that once gas hydrates formed, they show “memory effect†in subsequent charges, irrespective of the two gases injected. This was borne out by the induction time data for hydrate formation that reduced from 96 hours for CH4 and 24 hours for CO2 to instant hydrate formation in both cases upon injection of a secondary gas. During the study of CH4-CO2 exchange where CH4 hydrates were first formed and CO2 gas was injected into the system, gas chromatographic (GC) analysis of the cell indicated a pure CH4 gas phase, i.e. | all injected CO2 gas entered the hydrate phase and remained trapped in hydrate cages for several hours, though over time some CO2 did enter the gas phase. Alternatively, during the CH4-CO2 exchange study where CO2 hydrates were first formed, the injected CH4 initially entered the hydrate phase, but quickly gaseous CO2 exchanged with CH4 in hydrates to form more stable CO2 hydrates. These results are consistent with the better thermodynamic stability of CO2 hydrates, and this appears to be a promising method to sequester CO2 in natural CH4 hydrate matrices. The macroscale study described above was complemented by a microscale study to visualize hydrate growth. This first-of-its-kind in-situ study utilized the x-ray computed microtomography (CMT) technique to visualize microscale CO2, CH4, and mixed CH4-CO2 hydrate growth phenomenon in salt solutions in the presence or absence of porous media. The data showed that under the experimental conditions used, pure CH4 formed CH4 hydrates as mostly spheres, while pure CO2 hydrates were more dendritic branches. Additionally, varying ratios of mixed CH4-CO2 hydrates were also formed that had needle-like growth. In porous media, CO2 hydrates grew, consistent with known growth models in which the solution was the sediment wetting phase. When glass beads and Ottawa sand were used as a host, the system exhibited pore-filling hydrate growth, while the presence of liquid CO2 and possible CO2 hydrates in Ottawa sand initially were pore-filling that over time transformed into a grain-displacing morphology. The data appears promising to develop a method that would supplant our energy supply by extracting CH4 from naturally occurring hydrates while CO2 is sequestered in the same formations. | 303 pages

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