Hydraulically fractured shale formations are being developed widely for oil and gas production. They could also represent an attractive repository for permanent geologic carbon sequestration. Shales have a low permeability, but they can adsorb an appreciable amount of CO2 on fracture surfaces. Here, a computational method is proposed for estimating the CO2 sequestration capacity of a fractured shale formation and it is applied to the Marcellus shale in the eastern United States. The model is based on historical and projected CH4 production along with published data and models for CH4/CO2 sorption equilibria and kinetics. The results suggest that the Marcellus shale alone could store between 10.4 and 18.4 Gt of CO2 between now and 2030, which represents more than 50% of total U.S. CO2 emissions from stationary sources over the same period. Other shale formations with comparable pressure-temperature conditions, such as Haynesville and Barnett, could provide significant additional storage capacity. The mass transfer kinetic results indicate that injection of CO2 would proceed several times faster than production of CH4. Additional considerations not included in this model could either reinforce (e.g., leveraging of existing extraction and monitoring infrastructure) or undermine (e.g., leakage or seismicity potential) this approach, but the sequestration capacity estimated here supports continued exploration into this pathway for producing carbon neutral energy.

Hydrated mineral surfaces in the environment are generally hydrophilic but in certain cases can strongly adhere CO2, which is largely nonpolar. This adhesion can significantly alter the wettability characteristics of the mineral surface and consequently influence capillary/residual trapping and other multiphase flow processes in porous media. Here, the conditions influencing adhesion between CO2 and homogeneous mineral surfaces were studied using static pendant contact angle measurements and captive advancing/receding tests. The prevalence of adhesion was sensitive to both surface roughness and aqueous chemistry. Adhesion was most widely observed on phlogopite mica, silica, and calcite surfaces with roughness on the order of ~10 nm. The incidence of adhesion increased with ionic strength and CO2 partial pressure. Adhesion was very rarely observed on surfaces equilibrated with brines containing strong acid or base. In advancing/receding contact angle measurements, adhesion could increase the contact angle by a factor of 3. These results support an emerging understanding of adhesion of, nonpolar nonaqueous phase fluids on mineral surfaces influenced by the properties of the electrical double layer in the aqueous phase film and surface functional groups between the mineral and CO2.

The Fe nanoparticles dispersed in polyethylene glycol (PEG) can catalyze Fischer-Tropsch (F-T) synthesis at mild conditions (150 • C, 2.0 MPa H 2 , 1.0 MPa CO) with an activity as high as 1.5 mol CO mol Fe -1 h -1 . The F-T products, hydrocarbons, are insoluble in the green solvent PEG, and could be easily separated from the reaction mixture.