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  • 1
    Publication Date: 2020-02-06
    Description: The knowledge of the phase behavior of carbon dioxide (CO2)-rich mixtures is a key factor to understand the chemistry and migration of natural volcanic CO2 seeps in the marine environment, as well as to develop engineering processes for CO2 sequestration coupled to methane (CH4) production from gas hydrate deposits. In both cases, it is important to gain insights into the interactions of the CO2-rich phase—liquid or gas—with the aqueous medium (H2O) in the pore space below the seafloor or in the ocean. Thus, the CH4-CO2 binary and CH4-CO2-H2O ternary mixtures were investigated at relevant pressure and temperature conditions. The solubility of CH4 in liquid CO2 (vapor-liquid equilibrium) was determined in laboratory experiments and then modelled with the Soave–Redlich–Kwong equation of state (EoS) consisting of an optimized binary interaction parameter kij(CH4-CO2) = 1.32 × 10−3 × T − 0.251 describing the non-ideality of the mixture. The hydrate-liquid-liquid equilibrium (HLLE) was measured in addition to the composition of the CO2-rich fluid phase in the presence of H2O. In contrast to the behavior in the presence of vapor, gas hydrates become more stable when increasing the CH4 content, and the relative proportion of CH4 to CO2 decreases in the CO2-rich phase after gas hydrate formation.
    Type: Article , PeerReviewed
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  • 2
    Publication Date: 2021-03-18
    Description: This article presents gas hydrate experimental measurements for mixtures containing methane (CH4), carbon dioxide (CO2) and nitrogen (N2) with the aim to better understand the impact of water (H2O) on the phase equilibrium. Some of these phase equilibrium experiments were carried out with a very high water-to-gas ratio that shifts the gas hydrate dissociation points to higher pressures. This is due to the significantly different solubilities of the different guest molecules in liquid H2O. A second experiment focused on CH4-CO2 exchange between the hydrate and the vapor phases at moderate pressures. The results show a high retention of CO2 in the gas hydrate phase with small pressure variations within the first hours. However, for our system containing 10.2 g of H2O full conversion of the CH4 hydrate grains to CO2 hydrate is estimated to require 40 days. This delay is attributed to the shrinking core effect, where initially an outer layer of CO2-rich hydrate is formed that effectively slows down the further gas exchange between the vapor phase and the inner core of the CH4-rich hydrate grain.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2019-01-15
    Description: The recovery of natural gas from CH4-hydrate deposits in sub-marine and sub-permafrost environments through injection of CO2 is considered a suitable strategy towards emission-neutral energy production. This study shows that the injection of hot, supercritical CO2 is particularly promising. The addition of heat triggers the dissociation of CH4-hydrate while the CO2, once thermally equilibrated, reacts with the pore water and is retained in the reservoir as immobile CO2-hydrate. Furthermore, optimal reservoir conditions of pressure and temperature are constrained. Experiments were conducted in a high-pressure flow-through reactor at different sediment temperatures (2 °C, 8 °C, 10 °C) and hydrostatic pressures (8 MPa, 13 MPa). The efficiency of both, CH4 production and CO2 retention is best at 8 °C, 13 MPa. Here, both CO2- and CH4-hydrate as well as mixed hydrates can form. At 2 °C, the production process was less effective due to congestion of transport pathways through the sediment by rapidly forming CO2-hydrate. In contrast, at 10 °C CH4 production suffered from local increases in permeability and fast breakthrough of the injection fluid, thereby confining the accessibility to the CH4 pool to only the most prominent fluid channels. Mass and volume balancing of the collected gas and fluid stream identified gas mobilization as equally important process parameter in addition to the rates of methane hydrate dissociation and hydrate conversion. Thus, the combination of heat supply and CO2 injection in one supercritical phase helps to overcome the mass transfer limitations usually observed in experiments with cold liquid or gaseous CO2.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2019-09-23
    Description: The accumulation of methane hydrate in marine sediments is controlled by a number of physical and biogeochemical parameters including the thickness of the gas hydrate stability zone (GHSZ), the solubility of methane in pore fluids, the accumulation of particulate organic carbon at the seafloor, the kinetics of microbial organic matter degradation and methane generation in marine sediments, sediment compaction and the ascent of deep-seated pore fluids and methane gas into the GHSZ. Our present knowledge on these controlling factors is discussed and new estimates of global sediment and methane fluxes are provided applying a transport-reaction model at global scale. The modeling and the data evaluation yield improved and better constrained estimates of the global pore volume within the modern GHSZ ( ≥ 44 × 1015 m3), the Holocene POC accumulation rate at the seabed (~1.4 × 1014 g yr−1), the global rate of microbial methane production in the deep biosphere (4−25 × 1012 g C yr−1) and the inventory of methane hydrates in marine sediments ( ≥ 455 Gt of methane-bound carbon).
    Type: Article , PeerReviewed
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  • 5
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    ECO2 Project Office
    In:  ECO2 Deliverable, D12.2 . ECO2 Project Office, 6 pp.
    Publication Date: 2019-03-11
    Description: In order to proceed with speculative modelling of the impacts of potential leakage of geologically stored carbon, it is necessary to develop plausible scenarios. Here a range of such scenarios are developed based on a consensus of the possible geological mechanisms of leakage, namely abandoned wells, geological faults and operational blowouts. Whilst the resulting scenarios remain highly speculative, they do enable short term progress in modelling and provide a basis for further debate and refinement.
    Type: Report , NonPeerReviewed , info:eu-repo/semantics/book
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  • 6
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    ECO2 Project Office
    In:  ECO2 Deliverable, D12.1 . ECO2 Project Office, 14 pp.
    Publication Date: 2019-03-11
    Type: Report , NonPeerReviewed , info:eu-repo/semantics/book
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  • 7
    Publication Date: 2019-03-11
    Type: Report , NonPeerReviewed , info:eu-repo/semantics/book
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  • 8
    Publication Date: 2019-03-11
    Type: Report , NonPeerReviewed , info:eu-repo/semantics/book
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  • 9
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    China Geological Survey
    In:  [Paper] In: 8. International Conference on Gas Hydrates (ICGH8), 28.07.-01.08.2014, Beijing, China . Proceedings of the 8th International Conference on Gas Hydrates (ICGH8-2014), Beijing, China, 28 July - 1 August, 2014 ; T3-56 .
    Publication Date: 2016-12-21
    Description: Injection of CO2 into CH4-hydrate bearing sediments, and the resulting in-situ replacement of CH4-hydrate by CO2-hydrate, has been proposed as a technique for the emission-free production of natural gas from gas hydrates. While the hydrate conversion is thermodynamically feasible, many studies conclude that the overall process suffers from mass transfer limitations and CH4 production is limited after short time. To improve CH4 production various technical concepts have been considered, including the injection of heated supercritical CO2 combining chemical activation and thermalstimulation. While the feasibility of the concept was demonstrated in high-pressure flow-through experiments and high CH4 production efficiencies were observed, it was evident that overall yields and efficiencies were influenced by a variety of processes which could not be disclosed through bulk mass and volume analysis. Here we present different numerical simulation strategies which were developed and tested as tools to better understand the importance of mass and heat transport relative to reaction and phase transition kinetics for CH4 release and production, or for CO2 retention, respectively. The modeling approaches are discussed with respect to applicability for experimental design, process development or prediction of CH4 production from natural gas hydrate reservoirs on larger scales.
    Type: Conference or Workshop Item , NonPeerReviewed
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  • 10
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    China Geological Survey
    In:  [Paper] In: 8. International Conference on Gas Hydrates (ICGH8), 28.07.-01.08.2014, Beijing, China . Proceedings of the 8th International Conference on Gas Hydrates (ICGH8) Beijing, China, 28 July - 1 August, 2014 ; T1-68 .
    Publication Date: 2014-11-21
    Description: Water permeability in gas hydrate bearing sediments is a crucial parameter for the prediction of gas production scenarios. So far, the commonly used permeability models are backed by very few experimental data. Furthermore, detailed knowledge of the exact formation mechanism leads to severe uncertainties in the interpretation of the experimental data. We formed CH4 hydrates from a methane saturated water solution and used Magnetic Resonance Imaging (MRI) to measure time resolved maps of the three-dimensional gas hydrate saturation. These maps were used for 3D Finite Elements Method (FEM) simulations. The simulation results enabled us to optimize existing models for permeabilities as function of gas hydrate saturation.
    Type: Conference or Workshop Item , NonPeerReviewed
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