Effect of oxygen co-injected with carbon dioxide on Gothic shale caprock-CO_2-brine interaction during geologic carbon sequestration

摘要

Co-injection of oxygen, a significant component in CO_2 streams produced by the oxyfuel combustion process, can cause a significant alteration of the redox state in deep geologic formations during geologic carbon sequestration. The potential impact of co-injected oxygen on the interaction between synthetic CO_2-brine (0.1M NaCl) and shale caprock (Gothic shale from the Aneth Unit in Utah) and mobilization of trace metals was investigated at ~10MPa and ~75°C. A range of relative volume percentages of O_2 to CO_2 (0, 1, 4 and 8%) were used in these experiments to address the effect of oxygen on shale-CO_2-brine interaction under various conditions. Major mineral phases in Gothic shale are quartz, calcite, dolomite, montmorillonite, and pyrite. During Gothic shale-CO_2-brine interaction in the presence of oxygen, pyrite oxidation occurred extensively and caused enhanced dissolution of calcite and dolomite. Pyrite oxidation and calcite dissolution subsequently resulted in the precipitation of Fe(III) oxides and gypsum (CaSO_4·2H_2O). In the presence of oxygen, dissolved Mn and Ni were elevated because of oxidative dissolution of pyrite. The mobility of dissolved Ba was controlled by barite (BaSO_4) precipitation in the presence of oxygen. Dissolved U in the experimental brines increased to ~8-14μg/L, with concentrations being slightly higher in the absence of oxygen than in the presence of oxygen. Experimental and modeling results indicate the interaction between shale caprock and oxygen co-injected with CO_2 during geologic carbon sequestration can exert significant impacts on brine pH, solubility of carbonate minerals, stability of sulfide minerals, and mobility of trace metals. The major impact of oxygen is most likely to occur in the zone near CO_2 injection wells where impurity gases can accumulate. Oxygen in CO_2-brine migrating away from the injection well will be continually consumed through the reactions with sulfide minerals in deep geologic formations.