Experimental evaluation of cement integrity on exposure to supercritical CO₂ using NMR: Application to geostorage

Carbon sequestration is one approach to achieve carbon dioxide reduction in the atmosphere. Underground storage of CO requires an understanding of geochemical and geomechanical alteration on the integrity of the injection wellbore. In this study, we investigate the reactivity of supercritical CO (scCO) at 65 °C and 20.7 MPa on Portland class G cement plugs used for oil and gas well completion, for exposure of up to 5 weeks. For nanoporous media, such as cement, diffusion is believed to be the major mass transport mechanism (Perkins and Johnston, 1963) [1]. To quantify the extent of the alteration (mineralization/dissolution) on fluid diffusivity through the cement matrix, a novel approach based on Nuclear Magnetic Resonance (NMR) is employed to derive diffusional tortuosity. Comparing pre- and post-scCO exposure, deuterium oxide (DO) intrusion profiles allow us to determine flow path alteration in the cement plugs. Additional characterizations include Fourier Transform Infrared Spectroscopy (FTIR) to observe the change in cement composition, micro X-ray Computed Tomography (μXCT), along with Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) to determine invasion extent and microstructure modifications, Mercury Injection Capillary Pressure (MICP) for pore throat size distribution and BET N isothermal adsorption for surface area and pore size distribution. The results show that exposure to scCO promotes both calcium carbonate precipitation and dissolution simultaneously. However, the alteration is pore size dependent. After 5 weeks of exposure, there is evidence of carbonate dissolution in smaller pores (<30 nm) and both precipitation and dissolution in larger pores (30-200 nm). The alteration of the cement plugs leads to a decrease in the storage and connectivity of the cement. The porosity decreased from 37 to 33 % in 5 weeks, while the matrix tortuosity increased by 6 and 3 times after 2 and 5 weeks of exposure, respectively. The experimental results imply that the cement carbonate precipitation can limit the migration of scCO through the cement matrix. This work also highlights an alternative laboratory approach to quantify the risk associated with scCO₂ exposure on Portland cement using NMR-derived tortuosity.