Coupling amino acid injection and slow depressurization with hydrate swapping exploitation: An effective strategy to enhance in-situ CO2 storage in hydrate-bearing sediment

Natural gas (mainly methane, CH4) hydrates are a prospective energy resource. CH4-CO2 hydrate swapping has the advantages of producing CH4 gas for clean energy recovery and simultaneously storing CO2 in-situ for carbon emission reduction. Depressurization is the most feasible strategy to recover CH4 from hydrate-bearing sediments. The combination of these two methods has been proved feasible to produce CH4-rich gas and store CO2-rich hydrate. However, the efficiencies of CH4 recovery and CO2 storage decrease significantly when the reservoir is depressurized to the points below CH4/CO2 mixed hydrate equilibrium pressure causing unwanted CO2-rich hydrate dissociation. In this work, amino acid injection (AAI) (L-tryptophan or L-methionine) was employed for CH4/CO2 mixed hydrate formation with enhanced CO2 storage, followed by slow depressurization in various controlled manners, i.e., multistep depressurization, constant-pressure depressurization or multistep constant-pressure depressurization (MCPD) to recover CH4 from the mixed hydrates. In-situ Raman and gas chromatograph (GC) were employed to confirm the compositions of mixed hydrates formed and mixed gases produced. The results showed that AAI decreased CO2 fraction from 30 mol% to 3.1–8.4 mol% in the residual gas, indicating the technique helped regaining reservoir pressure and kinetically promoting further hydrate formation. The pressure recovered by AAI compensated the performance discrepancy caused by different solutions injected. Raman spectra and GC results confirmed CO2-rich hydrate formation, and up to 91.3% CO2 was stored in the sediments. During mixed hydrate dissociation, slow depressurization maintained high CH4-rich gas production (CH4 fraction over 87.5 mol%), with 9.7–30.6% CH4-rich gas recovered and 5.8–17.9% water produced among various trials. The best performance of CO2 storage and CH4 recovery was achieved by AAI of 1000 ppm L-tryptophan at 33.2 bar and MCPD to 20.9 bar, showing a final CO2 storage efficiency of 82.3%, gas recovery percentage of 30.6% and gas/water production ratio of 37.9 STP m3/m3. These findings provided guidance to enhance CO2-rich hydrate storage and CH4-rich gas production by multiple AAI and slow depressurization at controlled depletion pressures after hydrate swapping.