Multi-scale Analysis of Methane Gas Hydrate Formation and Dissociation via Point Source Thermal Stimulation and Carbon Dioxide Exchange
Creators: Fitzgerald, Garrett Christopher
Publisher: name: Columbia University
Year: 2014
Subjects: subject: Chemical engineering
subject: FOS: Chemical engineering

description: The formation and dissociation of methane gas hydrate was investigated over a range of laboratory scale systems with sample volumes of 1.3 cm3, 0.059 m3 and 0.141 m3. Three unique hydrate apparatuses were used to study a point source thermal dissociation method in which gas production profiles and cumulative efficiencies were found to be dependent on the initial hydrate saturation and the degree of thermal stimulation. Hydrate growth was observed to develop in a non-homogeneous manner with hydrate distribution displaying strong apparatus specific behavior. Heterogeneous hydrate distribution contributed to the production efficiencies of point source thermal stimulation and is an essential parameter when evaluating a gas hydrate reservoir. Thermal stimulation was applied to sediments with initial pore space hydrate saturations ranging from 10% to 80% producing maximum cumulative thermal production efficiencies ranging from 57% to 90%. Production performance was improved with higher initial hydrate saturation; increasing the initial hydrate saturation from 20% to 35% on the small scale system raised peak cumulative efficiencies from 57-63% to 70-74%. Increasing hydrate saturation from 10% to 30% in the medium scale system increased peak cumulative efficiencies from 83% to 90%. 
During thermal stimulation experiments in both the medium and large scale reactors a flow recirculation pattern developed within the pore space following an initially conduction dominated heat transfer regime. The outward propagation of the heat front from the heating element resulted in increased permeability and the release of mobile water and gas phases as the hydrate underwent dissociation. This change in flow parameters facilitated convection cells within the reactor causing increased heat transfer away from the heating element while displaying a strong upward bias. The flow development detected within the medium scale system was confirmed via history matching of numerical simulation with experimental data. Increased hydrate saturation and increased heating rate lead to a more intense flow development. 
Thermal stimulation methane production has been coupled with the simultaneous injection of gaseous carbon dioxide as method of enhancing gas production rates while providing a means for long term storage of carbon dioxide in the hydrate phase. The exchange process was investigated at low and high gas injection rates under conditions of both low and high thermal stimulation applied to a 50% hydrate saturated quartz sand pack. The amount of carbon dioxide stored in the hydrate phased was greatest for the low injection-high heating condition sequestering 69 moles, and lowest for the high injection- low heating condition sequestering 13 moles. The gas exchange is improved with longer contact time between gas phase carbon dioxide and hydrate phase methane, this condition is optimized at low carbon dioxide injection rates. The availability of free water for formation of carbon dioxide is enhanced with the higher heating rates. Thus it is possible to tune the gas production rates and carbon dioxide storage potential by manipulating heating rates and gas injection rates to achieve the desired ratio between methane produced and carbon dioxide sequestered. 
Understanding the transition period and flow development within the pore fluid mixture should play a large role in determining the optimum placement and geometry of heating and exchange systems on industrial scale hydrate production scenarios. In addition to the optimization of thermal stimulation heating location, the profile and degree of heating rate can be tuned in order to maximize gas collection and minimize excessive heating of unproductive sediment matrix after it has been exhausted of methane hydrate. The production efficiency produced across the three experimental scales averaged between 80 and 90% and appears to be independent of scale. The scale up of this method for industrial scale production should pay close attention to the distribution of heat during thermal stimulation as a result of the development of high convective transport that occurs in the near vicinity of the heater and in the dissociated hydrate zone. This work provides supportive evidence that thermal based hydrate dissociation can be achieved with relatively high production efficiencies and satisfactory resource recovery potentials. Further, the CH4-CO2 gas exchange process was successfully coupled with point source thermal stimulation and the influence of injection rate and heating rate on carbon storage potential and methane recovery potential has been demonstrated.