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Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids


Miller QRS, CJ Thompson, JS Loring, CF Windisch, Jr, ME Bowden, DW Hoyt, JZ Hu, BW Arey, KM Rosso, and HT Schaef.  2013.  "Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids."  International Journal of Greenhouse Gas Control 15:104-118.  doi:10.1016/j.ijggc.2013.02.005

Journal Article


Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratory research has been conducted on reactions occurring between minerals in the host rock and the wet supercritical fluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite but structurally amorphous. In addition, evidence of an intermediate hydrated amorphous calcium carbonate forming under these conditions further emphasize the importance of understanding geochemical processes occurring in water bearing scCO2 fluids.


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