Abstract

Managing impure carbon dioxide produced by fossil fuel-based generation of electricity is required for successful implementation of carbon capture, utilization, and storage. Impurities in carbon dioxide, particularly SOx and NOx, are geochemically more reactive than the carbon dioxide and may adversely impact a carbon dioxide storage reservoir by generating additional acidity. Hydrothermal experiments are performed to evaluate geochemical and mineralogic effects of injecting SO2-CO2 fluid into a carbonate reservoir. The experimental design is based on a natural carbon dioxide reservoir, the Madison Limestone on the Moxa Arch of Southwest Wyoming, which serves as a natural analog for geologic cosequestration of sulfur dioxide and carbon dioxide. Idealized Madison Limestone (dolomite+calcite±anhydrite+pyrite) and Na-Cl-SO42 brine (I=0.5  molal, initial pH=8.5) reacted at reservoir conditions (110°C and 25 MPa) for approximately 165 days (3960 h). Carbon dioxide fluid containing 500 ppmv sulfur dioxide was injected and the experiment continued for approximately 55 days (1326 h). Sulfur dioxide partitions out of the supercritical carbon dioxide phase and dissolves into coexisting brine on the time scale of the experiments (55 days). Injecting supercritical SO2-CO2 or pure supercritical carbon dioxide into a brine-limestone system produces the same in situ pH (4.6) and ex situ pH (6.4–6.5), as measured 28 h after injection because dissolution of calcite buffers in situ pH. Precipitation of anhydrite sequesters injected sulfur and, coupled with dissolution of calcite, effectively buffers the amount of dissolved calcium to the same concentrations measured in limestone-brine experiments injected with pure carbon dioxide. Supercritical SO2-CO2 does not enhance the sequestration potential of a carbonate reservoir relative to pure supercritical carbon dioxide. Our results substantiate predictions from natural analog studies of the Madison Limestone that anhydrite traps sulfur and carbonate minerals ultimately reprecipitate and mineralize carbon in carbonate reservoirs.

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