Washington University in St. Louis Washington University Open Scholarship Engineering and Applied Science Theses & McKelvey School of Engineering Dissertations Summer 8-15-2017 Aluminosilicate Dissolution and Silicate Carbonation during Geologic CO2 Sequestration Yujia Min Washington University in St. Louis Follow this and additional works at: https://openscholarship.wustl.edu/eng_etds Part of the Environmental Engineering Commons, Geochemistry Commons, and the Geotechnical Engineering Commons Recommended Citation Min, Yujia, "Aluminosilicate Dissolution and Silicate Carbonation during Geologic CO2 Sequestration" (2017). Engineering and Applied Science Theses & Dissertations. 315. https://openscholarship.wustl.edu/eng_etds/315 This Dissertation is brought to you for free and open access by the McKelvey School of Engineering at Washington University Open Scholarship. It has been accepted for inclusion in Engineering and Applied Science Theses & Dissertations by an authorized administrator of Washington University Open Scholarship. For more information, please contact [email protected]. WASHINGTON UNIVERSITY IN ST. LOUIS School of Engineering & Applied Science Department of Energy, Environmental & Chemical Engineering Dissertation Examination Committee: Young-Shin Jun, Chair Richard Axelbaum Alexander Bradley John Fortner Daniel Giammar Sophia Hayes Aluminosilicate Dissolution and Silicate Carbonation during Geologic CO2 Sequestration by Yujia Min A dissertation presented to The Graduate School of Washington University in partial fulfillment of the requirements for the degree of Doctor of Philosophy August 2017 St. Louis, Missouri © 2017, Yujia Min Table of Contents List of Figures ................................................................................................................................ vi Acknowledgments.......................................................................................................................... ix Abstract .......................................................................................................................................... xi Chapter 1: Introduction ................................................................................................................... 1 1.1 Background ...................................................................................................................... 1 1.1.1 Geologic CO2 Sequestration ................................................................................................. 1 1.1.2 Dissolution and Precipitation at CO2–Water–Rock Interfaces ............................................. 2 1.1.3 Co-sequestration of CO2 and SO2 ......................................................................................... 4 1.1.4 Enhanced Oil Recovery ........................................................................................................ 4 1.2 Research Objectives ......................................................................................................... 5 1.2.1 Limitations of Previous Studies ............................................................................................ 5 1.2.2 Specific Objectives ............................................................................................................... 8 1.3 Dissertation Overview ...................................................................................................... 9 Chapter 2: Anorthite Dissolution under Conditions Relevant to Subsurface CO2 Injection: Effects of Na+, Ca2+, and Al3+ ................................................................................................................... 13 Abstract ..................................................................................................................................... 13 2.1 Introduction .................................................................................................................... 14 2.2 Experimental Section ..................................................................................................... 17 2.2.1 Minerals and chemicals ....................................................................................................... 17 2.2.2 Dissolution experiments under simulated GCS conditions ................................................. 17 2.3 Results and Discussion ................................................................................................... 20 2.3.1 Inhibited anorthite dissolution at high solid/liquid ratios .................................................... 21 2.3.2 Inhibited anorthite dissolution by Al3+ ................................................................................ 21 2.3.3 Inhibited anorthite dissolution by Na+ ................................................................................ 28 2.3.4 Inhibited anorthite dissolution by Ca2+ and its co-existence with Na+ ................................ 32 2.4 Environmental Implications: Subsurface CO2 Injection ................................................ 35 Supporting Information for Chapter 2 ....................................................................................... 38 Chapter 3: Effects of Na+ and K+ Exchange in Interlayers on Biotite Dissolution under Geologic CO2 Sequestration Conditions ...................................................................................................... 52 Abstract ..................................................................................................................................... 52 ii 3.1 Introduction .................................................................................................................... 53 3.2 Experimental Methods ................................................................................................... 55 3.2.1 Minerals sample preparation and chemicals ....................................................................... 55 3.2.2 Dissolution experiments under simulated GCS conditions ................................................. 56 3.3 Results and Discussion ................................................................................................... 59 3.3.1 Dissolution of biotite flakes ................................................................................................ 59 3.3.2 Dissolution of biotite powder .............................................................................................. 65 3.3.3 Dissolution of biotite powder pretreated with NaCl solution ............................................. 67 3.4 Environmental Implications ........................................................................................... 71 Supporting Information for Chapter 3 ....................................................................................... 74 Chapter 4: Plagioclase Dissolution during CO2-SO2 Co-sequestration: Effects of Sulfate .......... 82 Abstract ..................................................................................................................................... 82 4.1 Introduction .................................................................................................................... 83 4.2 Experimental Methods ................................................................................................... 86 4.2.1 Minerals and chemicals ....................................................................................................... 86 4.2.2 Dissolution experiments at simulated GCS conditions ....................................................... 86 4.2.3 Fourier transform infrared (FTIR) spectroscopy analyses and dynamic light scattering measurements ...................................................................................................................................... 88 4.2.4 DFT calculations ................................................................................................................. 91 4.2.5 Secondary mineral phase identification .............................................................................. 92 4.3 Results and Discussion ................................................................................................... 93 4.2.1 Effects of sulfate on plagioclase dissolution ....................................................................... 93 4.2.2 Adsorption of sulfate on anorthite surfaces ........................................................................ 95 4.2.3 Effects of sulfate on plagioclase dissolution in the presence of oxalate ............................. 99 4.2.4 Effects of sulfate on secondary mineral precipitation ....................................................... 100 4.4 Environmental Implications ......................................................................................... 102 Supporting Information for Chapter 4 ..................................................................................... 104 Chapter 5: Wollastonite Carbonation in Water-bearing Supercritical CO2: Effects of Particle Size ..................................................................................................................................................... 110 Abstract ................................................................................................................................... 110 5.1 Introduction .................................................................................................................. 111 5.2 Experimental Methods ................................................................................................