@phdthesis{Li2023,
  author    = {Li, Zhen},
  title     = {Formation of Sub-Permafrost Methane Hydrate Reproduced by Numerical Modeling},
  doi       = {10.25932/publishup-60330},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-603302},
  school      = {Universit{\"a}t Potsdam},
  pages     = {XII, 109},
  year      = {2023},
  abstract  = {Natural gas hydrates are ice-like crystalline compounds containing water cavities that trap natural gas molecules like methane (CH4), which is a potent greenhouse gas with high energy density. The Mallik site at the Mackenzie Delta in the Canadian Arctic contains a large volume of technically recoverable CH4 hydrate beneath the base of the permafrost. Understanding how the sub-permafrost hydrate is distributed can aid in searching for the ideal locations for deploying CH4 production wells to develop the hydrate as a cleaner alternative to crude oil or coal. Globally, atmospheric warming driving permafrost thaw results in sub-permafrost hydrate dissociation, releasing CH4 into the atmosphere to intensify global warming. It is therefore crucial to evaluate the potential risk of hydrate dissociation due to permafrost degradation. To quantitatively predict hydrate distribution and volume in complex sub-permafrost environments, a numerical framework was developed to simulate sub-permafrost hydrate formation by coupling the equilibrium CH4-hydrate formation approach with a fluid flow and transport simulator (TRANSPORTSE). In addition, integrating the equations of state describing ice melting and forming with TRANSPORTSE enabled this framework to simulate the permafrost evolution during the sub-permafrost hydrate formation. A modified sub-permafrost hydrate formation mechanism for the Mallik site is presented in this study. According to this mechanism, the CH4-rich fluids have been vertically transported since the Late Pleistocene from deep overpressurized zones via geologic fault networks to form the observed hydrate deposits in the Kugmallit-Mackenzie Bay Sequences. The established numerical framework was verified by a benchmark of hydrate formation via dissolved methane. Model calibration was performed based on laboratory data measured during a multi-stage hydrate formation experiment undertaken in the LArge scale Reservoir Simulator (LARS). As the temporal and spatial evolution of simulated and observed hydrate saturation matched well, the LARS model was therefore validated. This laboratory-scale model was then upscaled to a field-scale 2D model generated from a seismic transect across the Mallik site. The simulation confirmed the feasibility of the introduced sub-permafrost hydrate formation mechanism by demonstrating consistency with field observations. The 2D model was extended to the first 3D model of the Mallik site by using well-logs and seismic profiles, to investigate the geologic controls on the spatial hydrate distribution. An assessment of this simulation revealed the hydraulic contribution of each geological element, including relevant fault networks and sedimentary sequences. Based on the simulation results, the observed heterogeneous distribution of sub-permafrost hydrate resulted from the combined factors of the source-gas generation rate, subsurface temperature, and the permeability of geologic elements. Analysis of the results revealed that the Mallik permafrost was heated by 0.8-1.3 °C, induced by the global temperature increase of 0.44 °C and accelerated by Arctic amplification from the early 1970s to the mid-2000s. This study presents a numerical framework that can be applied to study the formation of the permafrost-hydrate system from laboratory to field scales, across timescales ranging from hours to millions of years. Overall, these simulations deepen the knowledge about the dominant factors controlling the spatial hydrate distribution in sub-permafrost environments with heterogeneous geologic elements. The framework can support improving the design of hydrate formation experiments and provide valuable contributions to future industrial hydrate exploration and exploitation activities.},
  language  = {en}
}
@phdthesis{Pan2022,
  author    = {Pan, Mengdi},
  title     = {Systematic studies on the thermodynamic properties of gas hydrates and their formation/dissociation/transformation behaviors},
  doi       = {10.25932/publishup-55476},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-554760},
  school      = {Universit{\"a}t Potsdam},
  pages     = {XX, 192},
  year      = {2022},
  abstract  = {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.},
  language  = {en}
}