CO2 Utilization and Storage in Shale Gas Reservoirs

Surging natural gas production from fractured shale reservoirs and the emerging concept of utilizing anthropogenic CO2 for secondary recovery and permanent storage is driving the need for understanding fundamental mechanisms controlling gas adsorption and desorption processes, mineral volume changes, and impacts to transmissivity properties. Early estimates indicate that between 10 and 30 gigatons of CO2 storage capacity may exist in the 24 shale gas plays included in current USGS assessments. However, the adsorption of gases (CO2, CH4, and SO2) is not well understood and appears unique for individual clay minerals. Using specialized experimental techniques developed at PNNL, pure clay minerals were examined at relevant pressures and temperatures during exposure to CH4, CO2, and mixtures of CO2-SO2. Adsorbed concentrations of methane displayed a linear behavior as a function of pressure as determined by a precision quartz crystal microbalance. Acid gases produced differently shaped adsorption isotherms, depending on temperature and pressure. In the instance of kaolinite, gaseous CO2 adsorbed linearly, but in the presence of supercritical CO2, surface condensation increased significantly to a peak value before desorbing with further increases in pressure. Similarly shaped CO2 adsorption isotherms derived from natural shale samples and coal samples have been reported in the literature. Adsorption steps, determined by density functional theory calculations, showed they were energetically favorable until the first CO2 layer formed, corresponding to a density of ~0.35 g/cm3. Interlayer cation content (Ca, Mg, or Na) of montmorillonites influenced adsorbed gas concentrations. Measurements by in situ x-ray diffraction demonstrate limited CO2 diffusion into the Na-montmorillonite interlayer spacing, with structural changes related to increased hydration. Volume changes were observed when Ca or Mg saturated montmorillonites in the 1W hydration state were exposed to supercritical CO2. Additional experiments were conducted with pressurized attenuated total reflectance infrared spectroscopy technique that tracked clay hydration, gas adsorption, and water concentrations in the fluids during exposure to CO2 and CH4. These fundamental physico-chemical data are being collected into a database for parameterization of multiphase flow and reactive transport simulations of the CO2 injection, trapping, and secondary methane in fractured shales.