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Gas hydrates are ice-like crystalline compounds made of water cavities that retain various types of guest molecules. Natural gas hydrates are CH4-rich but also contain higher hydrocarbons as well as CO2, H2S, etc. They are highly dependent of local pressure and temperature conditions. Considering the high energy content, natural gas hydrates are artificially dissociated for the production of methane gas. Besides, they may also dissociate in response to global warming. It is therefore crucial to investigate the hydrate nucleation and growth process at a molecular level. The understanding of how guest molecules in the hydrate cavities respond to warming climate or gas injection is also of great importance.
This thesis is concerned with a systematic investigation of simple and mixed gas hydrates at conditions relevant to the natural hydrate reservoir in Qilian Mountain permafrost, China. A high-pressure cell that integrated into the confocal Raman spectroscopy ensured a precise and continuous characterization of the hydrate phase during formation/dissociation/transformation processes with a high special and spectral resolution. By applying laboratory experiments, the formation of mixed gas hydrates containing other hydrocarbons besides methane was simulated in consideration of the effects from gas supply conditions and sediments. The results revealed a preferential enclathration of different guest molecules in hydrate cavities and further refute the common hypothesis of the coexistence of hydrate phases due to a changing feed gas phase. However, the presence of specific minerals and organic compounds in sediments may have significant impacts on the coexisting solid phases. With regard to the dissociation, the formation damage caused by fines mobilization and migration during hydrate decomposition was reported for the first time, illustrating the complex interactions between fine grains and hydrate particles. Gas hydrates, starting from simple CH4 hydrates to binary CH4—C3H8 hydrates and multi-component mixed hydrates were decomposed by thermal stimulation mimicking global warming. The mechanisms of guest substitution in hydrate structures were studied through the experimental data obtained from CH4—CO2, CH4—mixed gas hydrates and mixed gas hydrates—CO2 systems. For the first time, a second transformation behavior was documented during the transformation process from CH4 hydrates to CO2-rich mixed hydrates. Most of the crystals grew or maintained when exposed to CO2 gas while some others decreased in sizes and even disappeared over time. The highlight of the two last experimental simulations was to visualize and characterize the hydrate crystals which were at different structural transition stages. These experimental simulations enhanced our knowledge about the mixed gas hydrates in natural reservoirs and improved our capability to assess the response to global warming.
Development of geophysical methods to characterize methane hydrate reservoirs on a laboratory scale
(2015)
Gas hydrates are crystalline solids composed of water and gas molecules. They are stable at elevated pressure and low temperatures. Therefore, natural gas hydrate deposits occur at continental margins, permafrost areas, deep lakes, and deep inland seas. During hydrate formation, the water molecules rearrange to form cavities which host gas molecules. Due to the high pressure during hydrate formation, significant amounts of gas can be stored in hydrate structures. The water-gas ratio hereby can reach up to 1:172 at 0°C and atmospheric pressure. Natural gas hydrates predominantly contain methane. Because methane constitutes both a fuel and a greenhouse gas, gas hydrates are a potential energy resource as well as a potential source for greenhouse gas.
This study investigates the physical properties of methane hydrate bearing sediments on a laboratory scale. To do so, an electrical resistivity tomography (ERT) array was developed and mounted in a large reservoir simulator (LARS). For the first time, the ERT array was applied to hydrate saturated sediment samples under controlled temperature, pressure, and hydrate saturation conditions on a laboratory scale. Typically, the pore space of (marine) sediments is filled with electrically well conductive brine. Because hydrates constitute an electrical isolator, significant contrasts regarding the electrical properties of the pore space emerge during hydrate formation and dissociation. Frequent measurements during hydrate formation experiments permit the recordings of the spatial resistivity distribution inside LARS. Those data sets are used as input for a new data processing routine which transfers the spatial resistivity distribution into the spatial distribution of hydrate saturation. Thus, the changes of local hydrate saturation can be monitored with respect to space and time.
This study shows that the developed tomography yielded good data quality and resolved even small amounts of hydrate saturation inside the sediment sample. The conversion algorithm transforming the spatial resistivity distribution into local hydrate saturation values yielded the best results using the Archie-var-phi relation. This approach considers the increasing hydrate phase as part of the sediment frame, metaphorically reducing the sample’s porosity. In addition, the tomographical measurements showed that fast lab based hydrate formation processes cause small crystallites to form which tend to recrystallize.
Furthermore, hydrate dissociation experiments via depressurization were conducted in order to mimic the 2007/2008 Mallik field trial. It was observed that some patterns in gas and water flow could be reproduced, even though some setup related limitations arose.
In two additional long-term experiments the feasibility and performance of CO2-CH4 hydrate exchange reactions were studied in LARS. The tomographical system was used to monitor the spatial hydrate distribution during the hydrate formation stage. During the subsequent CO2 injection, the tomographical array allowed to follow the CO2 migration front inside the sediment sample and helped to identify the CO2 breakthrough.