1. 1 Mario J. Martinez Bayani Cardenas, Kirsten Chojnicki, Chang Da, David DiCarlo, Eric Guiltinan, Susan Hovorka, Chun Huh, Keith Johnston, Ijung Kim, Prasanna Krishnamurthy, Alec Kucala, Tip Meckel, Sid Senthinalthan, Luca Trevisan, Lichun Wang, Yifeng Wang, Hongkyu Yoon 1 Sandia National Laboratories 2 University of Texas at Austin March 3, 2016 SAND2016-1292 C

2. Challenge 1: Sustaining Large Storage Rates Challenge 2: Using pore space with unprecedented efficiency Challenge 3: Controlling undesired or unexpected behavior Theme 3: Buoyancy- Driven Multiphase Flow Multiphase flow and reactive transport at the pore scale CT high pressure CO 2 core flood experiments with and without nanoparticles Experimentally tested invasion percolation modeling of buoyancy driven flow Theme 3: Buoyancy-Driven Multiphase Flow 2 Senior PersonnelStudents and Post-Docs B. Cardenas: flow/transport in fractures D. DiCarlo: multiphase, nanoparticles S. Hovorka: field studies C. Huh: nanoparticle chemistry K. Johnston: nanoparticles coatings M. Martinez: fluid mechanics, transport T. Meckel: geology, multiphase flow Y. Wang: geochemistry, wetting H. Yoon: experiments/models flow & transport K. Chojnicki: experiments/models flow & transport C. Da: nanoparticle experiments E. Guiltinan: wetting experiments P. Krishnamurthy: IP flow models & experiments I. Kim: multiphase nanoparticle experiments A. Kucala: flow and transport numerical models S. Senthinalthan: core flood experiments L. Trevisan: multiphase models & experiments L. Wang: flow and mechanics in fractures

3. Theme 3 Objectives Storage Efficiency Improve sweep efficiency Controlling Emergence Prevent unwanted fracturing Sustaining Injectivity Control wellbore failure CHALLENGES Guide injection limits Predict mineral trapping Enhance capillary (ganglion) trapping Prevent unexpected migration of CO 2 Enhance permeability/avoid precipitation during injection Control pathway development Predict solubility trapping Develop pore-scale experiments and linked flow models to elucidate and quantify the physics controlling migration and trapping of CO 2 in geologic carbon storage. Develop linked experiments and flow models to understand impact of cm-scale heterogeneity on flow path topology and residual saturation levels of capillary trapped CO 2. Identify potential emergent flow behavior. Investigate nanoparticles for control of pathway development and to prevent unwanted CO 2 migration.

4. 4 MJ Martinez 1, MB Cardenas 2, KN Chojnicki 1, A Kucala 1, L Wang 2, Y Wang 1, H Yoon 1 1 Sandia National Laboratories 2 University of Texas at Austin March 3, 2016 SAND2016-1292 C

5. Challenge 1: Sustaining Large Storage Rates Challenge 2: Using pore space with unprecedented efficiency Challenge 3: Controlling undesired or unexpected behavior Theme 3: Buoyancy- Driven Multiphase Flow Multiphase flow and reactive transport at the pore scale CT high pressure CO 2 core flood experiments with and without nanoparticles Experimentally tested invasion percolation modeling of buoyancy driven flow Multiphase Flow and Transport: Pore to Single Fracture Scale 5 Senior Personnel Students and Post-Docs Bayani Cardenas: flow and transport in fractures Yifeng Wang: geochemistry, wetting Hongkyu Yoon: experimental & numerical flow and transport Mario Martinez: fluid mechanics, transport and geomechanics Kirsten Chojnicki: experimental & numerical flow/transport Alec Kucala: flow and transport numerical models Lichun Wang: flow and mechanics in discrete fractures

6. Theme 3: GCS Processes in This Activity 6 Caprock Caprock jointing & fracture flow Mineral trapping Precipitation / dissolution Pressure & buoyancy driven flow Capillary & buoyancy controlled CO 2 migration Challenges: Sustain large storage rates Use pore space efficiently Control emergent behavior Capillary trapping

7. Elucidate pore-scale multiphase flow and reactive transport phenomena controlling migration and trapping of CO 2 in geologic carbon storage (GCS) systems using novel experimental techniques, pore scale imaging, and fundamental physics-based models. Storage Efficiency Improve sweep efficiency Predict solubility trapping Controlling Emergence Prevent unwanted fracturing Control pathway development Sustaining Injectivity Control wellbore failure CHALLENGES Guide injection limits Predict mineral trapping Enhance capillary (ganglion) trapping Prevent unexpected migration of CO 2 Enhance permeabilty/avoid precipitation during injection Activity Objectives

8. Linked porescale experiments and models –Reactive microfluidics –Microhydrodynamics models Roughness –Apparent contact angle & permeability –Fracture permeability, contact stress, fracture stiffness Outline 8

9. Flow-Coupled Mineralization 9 CO 3 2- @ pH=~11 Precipitation stage: [Ca 2+ ] T =[CO 3 2- ] T =10 mM for 75 hrs Dissolution stage: pH=4 solution into both sides Snapshot 24 hrs after the dissolution stage Ca 2- @ pH=~6 Objective: Understand how mineralization couples to flow dynamics Dissolution yields mobile nano-particles similar to tracer transport Precipitate morphology depends on concentration gradient, flow rate, and evolving pore structure Chojnicki & Yoon

10. 3D Flow Visualization and Modeling 10 3D micro Particle Image Velocimetry (PIV) using Laser Scanning Confocal Microscopy modified from Lima et al. (2006) Steady, single-phase flow in micromodel Bottom Middle Top This calibration shows similar flow patterns at all depths, as expected Particles 3D pore structure Pore structure 3D flow field Our  PIV system is able to image 3D flows in evolving pore structures

11. Porescale Fluid Dynamics 11 Dynamic contact angle Computational models for dynamic wetting Contact angle varies with Ca Contact Line Dynamics Objectives First-principles based models of mesoscale multiphase flow to: –Develop macroscale Pc(Ca, M, Bo, heterogeneity,…) for ganglion dynamics –Remove modeling assumptions for improving abstracted models (IP, PN) –Identify mechanisms of emergent flow transition behavior Impact on Geological Carbon Storage Challenges 2 & 3: –Elucidate the physics of flow regime transition –Develop mechanistic understanding of ganglion formation, flow, interaction, fragmentation, and coalescence in heterogeneous media Experimental measurements High Ca droplets ride on a wetting film Dashed – CFD/MCL Solid -- Washburn g Kucala, Chojnicki, Guiltinan, Wang, Yoon, Cardenas, Martinez Capillary rise Washburn Models of low Ca dynamic wetting require contact line models Blake, 2006

12. Roughness Impacts Wettability 12 Shao et al. (2010) Examples of natural and/or reaction-induced roughness Roughness impacts apparent contact angle, … Wenzel Cassie-Baxter and induces apparent “slip” Young Kucala, Chojnicki, Wang, Yoon, Martinez Water Strider Herminghaus, (2000) Hu et al. (2013) Phlogopite

13. Super-Hydrophobicity Applied to Ganglion Dynamics 13 Lee et al. (2010) Rothstein (2010) Lee et al. (2010) Cassie-Baxter theory indicates roughness enhances ganglion trapping Super-hydrophobicity can be attained through engineered roughness Roughness

14. Effective Permeability and Slip on Rough Surfaces 14 Injected Fluid Trapped Fluid  Contact angle  Roughness periodicity (d/L)  Roughness amplitude (h/d)  Viscosity ratio Injected sCO2 Trapped Brine Injected Brine Trapped sCO2 d/L = 1.6 Periodic two-phase flow model Conceptual model of roughness Permeability slip (b) CO 2 Brine pore-scale roughness

15. Fracture Permeability and Closure Stiffness: Discrete Fracture Model 15 Motivation and Goal: Develop a coupled mechanics and hydrological model relating stress, fracture closure stiffness and fracture permeability. Methods: Utilize synthetic fractures in Hopkins fracture deformation model combined with modified Local Cubic Law. Hopkins deformation modelFracture closure Fracture stiffness Model demonstrates fracture specific stiffness is proportional to normal stress and contact area for fractures with aperture field following a normal distribution L. Wang & Cardenas

16. Fracture Permeability and Closure Stiffness: Discrete Fracture Model 16 Model suggests a scaling law relating stiffness and permeability across a broad range of roughness and correlation lengths.

17. Accomplishments: Reactive transport experiments demonstrate potential permeability manipulation. Reaction-induced hydrophobicity can enhance ganglion trapping. IP simulations can match meter-scale sand-pack experiments. Developed coated nanoparticles which stabilize CO 2 displacements; implies 100% increase in CO 2 storage possible. Developed new model coupling fracture closure, flow topology with normal stress. Storage Efficiency Improve sweep efficiency Predict solubility trapping Controlling Emergence Prevent unwanted fracturing Control pathway development Sustaining Injectivity Control wellbore failure CHALLENGES Guide injection limits Predict mineral trapping Enhance capillary (ganglion) trapping Prevent unexpected migration of CO 2 Enhance permeability/avoid precipitation during injection Summary Future Work: Validate mesoscale flow model with micromodel experiments at reservoir conditions. Develop cm-scale ganglion dynamics flow model utilizing porescale models and experiments. Validate fracture closure and flow topology model with experiment. Complete sand-tanks; flow regime experiments. Perform vertical nanoparticle-stabilized coreflood experiments; validate models.

18. Acknowledgements 18