Methane hydrate behavior when exposed to a 23% carbon dioxide 77% nitrogen gas under conditions similar to the ConocoPhillips 2012 Ignik Sikumi Gas Hydrate Field Trial

In-situ replacement of methane hydrate by carbon dioxide hydrate is considered to be a promising technique for producing natural gas, while simultaneously sequestering greenhouse gas in deep geological formations. For effective application of this technique in the field, kinetic models of gas exchange rates in hydrate under a variety of environmental conditions need to be established, and the impact of hydrate substitution on geophysical (seismic) properties has to be quantified in order to optimize monitoring techniques. We performed a series of laboratory tests in which we monitored changes in methane hydrate-bearing samples while a nitrogen/carbon dioxide gas mixture was flowed through. These experiments were conducted to gain insights into data obtained from a field test in which the same mixture of carbon dioxide and nitrogen was injected into a methane hydrate-bearing unit beneath the north slope of the Brooks Range in northern Alaska (ConocoPhillips 2012 Ignik Sikumi gas hydrate field trial). We have measured the kinetic gas exchange rate for a range of hydrate saturations and different test configurations, to provide an estimate for comparison to numerical model predictions. In our tests, the exchange rate decreased over time during the tests as methane was depleted from the system. Following the elution of residual gaseous methane, the exchange rate ranged from 3.8×10-7 moles methane/(mole water*s) to 5×10-8 moles methane/(mole water*s) (Note that in these rates, the moles of water refers to water originally held in the hydrate.). In addition to the gas exchange rate, we also monitored changes in permeability occurring due to the gas substitution. Further, we determined the seismic P and S wave velocities and attenuations using our Split Hopkinson Resonant Bar apparatus (e.g. Nakagawa, 2012, Rev. Sci. Instr.). In addition to providing geophysical signatures, changes in the seismic properties can also be related to changes in the mechanical strength of the hydrate-bearing sand resulting from exposure to the mixed gas. Upon introduction of the mixed gas, the sample became less stiff and wave attenuation increased, indicating the presence of liquid water between mineral grains and hydrate. Slow dissociation of hydrate conducted in this experiment showed a range of hydrate stability conditions as the gas composition changed from dissociation and dilution of the previously injected nitrogen.