Summary
Depleted gas fields are among the most probable candidates for subsurface storage of carbon dioxide (CO2). With proven reservoir and qualified seal, these fields have retained gas over geological time scales. However, unlike methane, injection of CO2 changes the pH of the brine because of the formation of carbonic acid. Subsequent dissolution/precipitation of minerals changes the porosity/permeability of reservoir and caprock. Thus, for adequate, safe, and effective CO2 storage, the subsurface system needs to be fully understood. An important aspect for subsurface storage of CO2 is purity of this gas, which influences risk and cost of the process. To investigate the effects of CO2 plus impurities in a real case example, we have carried out medium-term (30-day) laboratory experiments (300 bar, 100°C) on reservoir and caprock core samples from gas fields in the northeast of the Netherlands. In addition, we attempted to determine the maximum allowable concentration of one of the possible impurities in the CO2 stream [hydrogen sulfide (H2S)] in these fields.
The injected gases—CO2, CO2+100 ppm H2S, and CO2+5,000 ppm H2S—were reacting with core samples and brine (81 g/L Na+, 173 g/L Cl−, 22 g/L Ca2+, 23 g/L Mg2+, 1.5 g/L K+, and 0.2 g/L SO42−). Before and after the experiments, the core samples were analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD) for mineralogical variations. The permeability of the samples was also measured. After the experiments, dissolution of feldspars, carbonates, and kaolinite was observed as expected. In addition, we observed fresh precipitation of kaolinite. However, two significant results were obtained when adding H2S to the CO2 stream. First, we observed precipitation of sulfate minerals (anhydrite and pyrite). This differs from results after pure CO2 injection, where dissolution of anhydrite was dominant in the samples. Second, severe salt precipitation took place in the presence of H2S. This is mainly caused by the nucleation of anhydrite and pyrite, which enabled halite precipitation, and to a lesser degree by the higher solubility of H2S in water and higher water content of the gas phase in the presence of H2S. This was confirmed by the use of CMG-GEM (CMG 2011) modeling software.
The precipitation of halite, anhydrite, and pyrite affects the permeability of the samples in different ways. After pure CO2 and CO2+100 ppm H2S injection, permeability of the reservoir samples increased by 10–30% and ≤3%, respectively. In caprock samples, permeability increased by a factor of 3–10 and 1.3, respectively. However, after addition of 5,000 ppm H2S, the permeability of all samples decreased significantly. In the case of CO2+100 ppm H2S, halite, anhydrite, and pyrite precipitation did balance mineral dissolution, causing minimal variation in the permeability of samples.
An analytic nonlinear model of thermo-poro-elastic pressure transients in porous rocks 2 with application to deep CO2 storage.
