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.

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.

Description: The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. Currently, process conditions under which this goal can be achieved efficiently are largely unknown. While the recent Ignik Sikumi field test suggests that a combination of N2/CO2 injection with depressurization yields effective CH4 production, in a previous study (Deusner et al., 2012) we showed that a combination of CO2 injection and thermal stimulation eliminates mass transfer limitations observed at cold reservoir temperatures. These high-pressure flow-through studies revealed that the injection of supercritical CO2 at 95 °C triggers dissociation of CH4-hydrates and counters rapid CO2-hydrate formation in the near-injection region. We also observed a strong effect of reservoir temperature on CH4 production and CO2 retention. The efficiency and yield of CH4 production was highest at a sediment temperature of 8 °C compared to 2 °C and 10 °C. At 2 °C CO2 hydrate formation was rapid and clogged the sediment at the injection spot. Outside the CO2-hydrate stability region, at 10 °C, we observed fast CO2 breakthrough and a comparably low CH4 production. Experiments comparing discontinuous and continuous CO2 injection showed that alternating periods of equilibration and CO2 injection improved the overall CH4 production. We hypothesize that slow formation of secondary CO2-rich hydrate improves the accessibility of the CH4-hydrate distributed in the sediment by locally changing permeability and fluid flow patterns. In situ measurements showed dynamic changes of local p-/T-gradients due to gas hydrate dissociation or dissolution and secondary gas hydrate formation. In addition, continued reconfiguration of guest molecules in transiently formed mixed hydrates maintain elevated gas exchange kinetics. Online effluent fluid analysis under in-situ pressure conditions indicated that CH4 released from CH4-hydrates is largely dissolved in liquid CO2.. It is a current objective of our studies to further elucidate rheological properties and gas exchange efficiencies of CO2-CH4 mixed fluids that approach equilibrium with gas hydrates and to study the effect of in situ CH4-CO2-hydrate conversion and secondary gas hydrate formation on sediment geomechanical parameters.