Qinjun Kang

Capacitive deionization (CDI) is a promising technology that has gained interest for the desalination of brackish water. Hierarchically porous carbons are commonly used as electrodes for CDI due to their high surface areas and controlled pore size distributions that maximize ion adsorption capacity and rate. Electrospinning is an effective way of generating carbon nanofibers with high inter-fiber macroporosity that can be further modified to improve surface area, total pore volume, and pore size distribution. This work describes the use of sacrificial mesopore formers in tandem with a micropore etching technique to induce hierarchical porosity in electrospun fibers. Mesopores are formed via the dissolution of silica nanoparticles that are introduced into the fibers during the electrospinning step. After mesopore formation, micropores are etched into the resulting surface through KOH impregnation and thermal activation. This sequential technique creates a hierarchical network of pores from the inherent macroporosity of the fiber network, to the mesopores, and finally micropores to simultaneously maximize surface area and accessibility. Micropore formation is optimized to maximize specific surface area while maintaining physical integrity of the fibers. The combination of mesopores and micropores enables fast ion adsorption rates and capacity. Carbon fiber electrodes fabricated in this method achieve specific surface areas exceeding 1400 m2 g−1, with pore volumes exceeding 1.0 cc g−1. The pore size distributions are highly controlled, with 80 % of total pore volume coming from pores <20 nm in radius. In 500 ppm constant voltage CDI tests, these fiber electrodes obtain a salt adsorption capacity of over 14 mg g−1 at a salt adsorption rate of ∼4 mg g−1 min−1, showcasing the high capacity matched with high rate of these easily fabricated, inexpensive materials. •Hierarchically porous carbon fibers were prepared by electrospinning.•Fibers were tested as electrodes for capacitive deionization.•Pore scale modeling provided insights into effect of pore size distribution.•Optimization of mesopore and micropore content provided maximum performance

Controlling atmospheric warming requires immediate reduction of carbon dioxide (CO2) emissions, as well as the active removal and sequestration of CO2 from current point sources. One promising proposed strategy to reduce atmospheric CO2 levels is geologic carbon sequestration (GCS), where CO2 is injected into the subsurface and reacts with the formation to precipitate carbonate minerals. Rapid mineralization has recently been reported for field tests in mafic and ultramafic rocks. However, unlike saline aquifers and depleted oil and gas reservoirs historically considered for GCS, these formations can have extremely low porosities and permeabilities, limiting storage volumes and reactive mineral surfaces to the preexisting fracture network. As a result, coupling between geochemical interactions and the fracture network evolution is a critical component of long-term, sustainable carbon storage. In this paper, we summarize recent advances in integrating experimental and modeling approaches to determine the first-order processes for carbon mineralization in a fractured mafic/ultramafic rock system. We observe the critical role of fracture aperture, flow, and surface characteristics in controlling the quantity, identity, and morphology of secondary precipitates and present where the influence of these factors can be reflected in newly developed thermo-hydro-mechanical–chemical models. Our findings provide a roadmap for future work on carbon mineralization, as we present the most important system components and key challenges that we are overcoming to enable GCS in mafic and ultramafic rocks.

•A 3D model of multiphase reactive flow with solid dissolution is proposed.•The diagram of multiphase reactive flow including several patterns is established.•A new correlation of reactive surface area-porosity-saturation is formulated.•Different pore size distributions and bubble characteristics are quantified.•The mass transfer coefficient and effective reaction rate are evaluated. There are still many unclear mechanisms in the multiphase reactive flow with solid dissolution processes. In this study, the reactive transport processes coupled with solid dissolution and self-induced multiphase flow in three-dimensional (3D) structures with increasing complexity is studied by developing a 3D computational microfluidic method, which considers multiphase flow, interfacial mass transport, heterogeneous chemical reactions, and solid structure evolution. Solid dissolution diagram in a simple channel in the framework of multiphase flow is proposed, with six coupled multiphase flow and solid dissolution patterns identified and the transition between different patterns discussed. Then, multiphase reactive flow in a porous chip is further studied, and the interesting 3D phenomena are discovered, including enhanced solid dissolution in the middle and enriched bubble generation at the corner along the thickness direction. Considering the importance of reactive surface area, correlations of reactive surface area-porosity-saturation with different dissolution patterns are proposed based on the pore-scale results. Finally, the computational microfluidic model is extended to investigate the multiphase reactive flow in a 3D digital core. Different dissolution patterns are recognized using the local porosity evolution character, and the corresponding pore size distribution and bubble characteristics are deciphered. These findings advance understanding of multiphase reactive transport processes and contribute to improve continuum-scale reactive transport modeling. Computational microfluidic study of multiphase reactive flow with solid dissolution and bubble generation in a simple channel, a microfluidic porous chip, and a digital core. [Display omitted]

•A multiphase reactive transport pore-scale model is improved.•Negative feedback between multiphase flow and solid dissolution is revealed.•Multiphase flow can promote the compact solid dissolution in porous media.•Structure heterogeneity effect is not intensified in the multiphase dissolution.•A new correlation between porosity, saturation and interfacial length is proposed. Fundamental understanding of the multiphase reactive transport with solid dissolution is crucial for a wide range of scientific and engineering problems. In this study, a pore-scale model is improved to study coupled processes of multiphase flow, mass transport, chemical reaction and solid dissolution in porous media with increasing structural heterogeneity. The results show that with the existence of multiphase flow, under the reactive transport conditions studied (Pe = 5, Da = 10; and Pe = 5, Da = 1), more compact dissolution pattern is generated due to the negative feedback between reactant transport and solid dissolution, while the feedback is positive in single-phase condition leading to wormhole dissolution. Besides, while it is found that the structural heterogeneity amplifies the wormhole dissolution in single-phase reactive transport processes or promotes the formation of fingering for multiphase flow, such heterogeneity effect is homogenized in the multiphase case. Finally, based on the pore-scale results, a new correlation between porosity, saturation and interfacial length is proposed which can be upscaled into the continuum-scale models.

Relative permeability is a key parameter for characterizing the multiphase flow dynamics in porous media at macroscopic scale while it can be significantly impacted by wettability. Recently, it has been reported in microfluidic experiments that wettability is dependent on the pore size (Van Rooijen et al., 2022). To investigate the effect of pore‐size‐dependent wettability on relative permeability, we propose a theoretical framework informed by digital core samples to quantify the deviation of relative permeability curves due to wettability change. We find that the significance of impact is highly dependent on two factors: (i) the function between contact angle and pore size (ii) overall pore size distribution. Under linear function, this impact can be significant for tight porous media with a maximum deviation of 1,000%. Plain Language Summary Relative permeability is an important feature for multiphase flow at the reservoir scale. It can be highly dependent on wettability, which is an interfacial property at the pore scale. Recent experimental evidence suggests that wettability is dependent on the pore size, but the impact of the pore‐size‐dependent wettability on relative permeability still remains unknown. In this study, we propose a theoretical model to investigate the effect of pore‐size‐dependent wettability on relative permeability. The pore size distribution is informed by the pore images. We find that the impact can be significant for low‐permeability porous media under certain conditions. The results imply that this effect is not always neglible when modeling two‐phase flow. Key Points A theoretical framework is proposed to quantify the impact of pore‐size dependent wettability on relative permeability The maximum impact on relative permeability can be as significant as 1,000%

Uncertainty in geological models usually leads to large uncertainty in the predictions of risk- related system properties and/or risk metrics (e.g., CO2 plumes and CO2/brine leakage rates) at a geologic CO2 storage site. Different types of data (e.g., point measurements from monitoring wells and spatial data from 4D seismic surveys) can be leveraged or assimilated to reduce the risk predictions. In this work, we develop a novel framework for spatial data assimilation and risk forecasting. Under the U.S. Department of Energy's National Risk Assessment Partnership (NRAP), we have developed a framework using an ensemble- based data assimilation approach for spatial data assimilation and forecasting. In particular, we took CO2 saturation maps interpreted from 4D seismic surveys as inputs for spatial data assimilation. Three seismic surveys at Years 1, 3, and 5 were considered in this study. Accordingly, three saturation maps were generated for data assimilation. The impact from the level of data noise was also investigated in this work. Our results show increased similarity between the updated reservoir models and the "ground- truth" model with the increased number of seismic surveys. Predictive accuracy in CO2 saturation plume increases with the increased number of seismic surveys as well. We also observed that with the increase in the level of data noise from 1% to 10%, the difference between the updated models and the ground truth does not increase significantly. Similar observations were made for the prediction of CO2 plume distribution at the end of the CO2 injection period by increasing the data noise.

Geologic storage of CO2 and H2 are climate‐positive techniques for meeting the energy transition. While similar formations could be considered for both gases, the flow dynamics could differ due to differences in their thermophysical properties. We conduct a rigorous pore‐scale study of water/CO2 and water/H2 systems at relevant reservoir conditions in a Bentheimer rock sample using the lattice Boltzmann method to quantify the effects of capillary, viscous, inertial, and wetting forces during gas invasion. At similar conditions, H2 invasion is weaker compared to CO2 due to unfavorable viscosity ratios. Increasing flow rate, however, increases the breakthrough saturation for both gas systems in the range of capillary numbers studied. At isolated conditions of flow rate, viscosity ratio, and wettability, local inertial effects are found to be critical and show consistent increase in the invaded gas saturation. The effect of inertial forces persits for both gases across all field conditions tested. Plain Language Summary We present a numerical investigation at the pore‐scale to contrast the dynamics of fluid transport for water/CO2 and water/H2 systems at reservoir conditions. Understanding such dynamics is critical to evaluate the feasibility of the geologic storage of these gases (long‐term storage of CO2 and short‐term, periodic storage of H2), which are being researched as green techniques for mitigating climate change. Through a systematic analysis, we demonstrate the importance of pore‐scale mechanisms like local inertial effects which are not well studied in the literature. These effects cause fast fluid motion and consistently allow more fluid to be injected in the rock independently from the other physical effects. Such effects should be carefully accounted for when modeling these systems for large‐scale gas storage. Key Points At similar reservoir conditions, invasion of H2 is found to be weaker as opposed to CO2 due to unfavorable viscosity ratios Among the tested reservoir scenarios, P/T conditions for the saline aquifer provided the largest amount of invaded gas until breakthrough Local inertial effects control the dynamics of the invading gas across different wettability, viscosity ratios, and capillary numbers