Efficient Recovery of CO2 from Flue Gas by Clathrate Hydrate Formation in Porous Silica Gels

摘要

Thermodynamic measurements and NMR spectroscopic analysis were used to show that it is possible to recover CO2 from flue gas by forming a mixed hydrate that removes CO2 preferentially from CO2/N2 gas mixtures using water dispersed in the pores of silica gel. Kinetic studies with 1H NMR microimaging showed that the dispersed water in the silica gel pore system reacts readily with the gas, thus obviating the need for a stirred reactor and excess water. Hydrate phase equilibria for the ternary CO2-N2-water system in silica gel pores were measured, which show that the three-phase hydrate-water-rich liquid-vapor equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO2 in the vapor phase decreased. 13C cross-polarization NMR spectral analysis and direct measurement of the CO2 content in the hydrate phase suggested that the mixed hydrate is structure I at gas compositions of more than 10 mol % CO2, and that the CO2 molecules occupy mainly the more abundant 51262 cages. This makes it possible to achieve concentrations of more than 96 mol % CO2 gas in the product after three cycles of hydrate formation and dissociation. 1H NMR microimaging showed that hydrate yields of better than 85%, based on the amount of water, could be obtained in 1 h when a steady state was reached, although ~90% of this yield was achieved after ~20 min of reaction time.