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Title: Reaction and diffusion at the reservoir/shale interface during CO2 storage: Impact of geochemical kinetics

Abstract

Here we use a reactive diffusion model to investigate what happens to CO2 injected into a subsurface sandstone reservoir capped by a chlorite- and illite-containing shale seal. The calculations simulate reaction and transport of supercritical (SC) CO2 at 348.15 K and 30 MPa up to 20,000 a. Given the low shale porosity (5%), chemical reactions mostly occurred in the sandstone for the first 2000 a with some precipitation at the ss/sh interface. From 2000 to 4000 a, ankerite, dolomite and illite began replacing Mg–Fe chlorite at the sandstone/shale interface. Transformation of chlorite to ankerite is the dominant reaction occluding the shale porosity in most simulations: from 4000 to 7500 a, this carbonation seals the reservoir and terminates reaction. Overall, the carbonates (calcite, ankerite, dolomite), chlorite and goethite all remain close to local chemical equilibrium with brine. Quartz is almost inert from the point of its dissolution/precipitation. However, the rate of quartz reaction controls the long-term decline in aqueous silica activity and its evolution toward equilibrium. The reactions of feldspars and clays depend strongly on their reaction rate constants (microcline is closer to local equilibrium than albite). The timing of porosity occlusion mostly therefore depends on the kinetic constants of kaolinitemore » and illite. For example, an increase in the kaolinite kinetic constant by 0.25 logarithmic units hastened porosity closure by 4300 a. The earliest simulated closure of porosity occurred at approximately 108 a for simulations designed as sensitivity tests for the rate constants. These simulations also emphasize that the rate of CO2 immobilization as aqueous bicarbonate (solubility trapping) or as carbonate minerals (mineral trapping) in sandstone reservoirs depends upon reaction kinetics – but the relative fraction of each trapped CO2 species only depends upon the initial chemical composition of the host sandstone. For example, at the point of porosity occlusion the fraction of bicarbonate remaining in solution depends upon the initial Na and K content in the host rock but the fraction of carbonate mineralization depends only on the Ca, Mg, Fe content. Since ankerite is the dominant mineral that occludes porosity, the dissolved concentration of ferrous iron is also an important parameter. Finally, future efforts should focus on cross-comparisons and ground-truthing of simulations made for standard case studies as well as laboratory measurements of the reactivities of clay minerals.« less

Authors:
 [1];  [2];  [3];  [3];  [1]
+ Show Author Affiliations
  1. Pennsylvania State Univ., University Park, PA (United States). Earth and Environmental Systems Inst.
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1482171
Grant/Contract Number:  
FE0004000
Resource Type:
Accepted Manuscript
Journal Name:
Applied Geochemistry
Additional Journal Information:
Journal Volume: 61; Journal ID: ISSN 0883-2927
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES

Citation Formats

Balashov, Victor N., Guthrie, George D., Lopano, Christina L., Hakala, J. Alexandra, and Brantley, Susan L. Reaction and diffusion at the reservoir/shale interface during CO2 storage: Impact of geochemical kinetics. United States: N. p., 2015. Web. doi:10.1016/j.apgeochem.2015.05.013.
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Balashov, Victor N., Guthrie, George D., Lopano, Christina L., Hakala, J. Alexandra, & Brantley, Susan L. Reaction and diffusion at the reservoir/shale interface during CO2 storage: Impact of geochemical kinetics. United States. https://doi.org/10.1016/j.apgeochem.2015.05.013
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Balashov, Victor N., Guthrie, George D., Lopano, Christina L., Hakala, J. Alexandra, and Brantley, Susan L. Wed . "Reaction and diffusion at the reservoir/shale interface during CO2 storage: Impact of geochemical kinetics". United States. https://doi.org/10.1016/j.apgeochem.2015.05.013. https://www.osti.gov/servlets/purl/1482171.
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@article{osti_1482171,
title = {Reaction and diffusion at the reservoir/shale interface during CO2 storage: Impact of geochemical kinetics},
author = {Balashov, Victor N. and Guthrie, George D. and Lopano, Christina L. and Hakala, J. Alexandra and Brantley, Susan L.},
abstractNote = {Here we use a reactive diffusion model to investigate what happens to CO2 injected into a subsurface sandstone reservoir capped by a chlorite- and illite-containing shale seal. The calculations simulate reaction and transport of supercritical (SC) CO2 at 348.15 K and 30 MPa up to 20,000 a. Given the low shale porosity (5%), chemical reactions mostly occurred in the sandstone for the first 2000 a with some precipitation at the ss/sh interface. From 2000 to 4000 a, ankerite, dolomite and illite began replacing Mg–Fe chlorite at the sandstone/shale interface. Transformation of chlorite to ankerite is the dominant reaction occluding the shale porosity in most simulations: from 4000 to 7500 a, this carbonation seals the reservoir and terminates reaction. Overall, the carbonates (calcite, ankerite, dolomite), chlorite and goethite all remain close to local chemical equilibrium with brine. Quartz is almost inert from the point of its dissolution/precipitation. However, the rate of quartz reaction controls the long-term decline in aqueous silica activity and its evolution toward equilibrium. The reactions of feldspars and clays depend strongly on their reaction rate constants (microcline is closer to local equilibrium than albite). The timing of porosity occlusion mostly therefore depends on the kinetic constants of kaolinite and illite. For example, an increase in the kaolinite kinetic constant by 0.25 logarithmic units hastened porosity closure by 4300 a. The earliest simulated closure of porosity occurred at approximately 108 a for simulations designed as sensitivity tests for the rate constants. These simulations also emphasize that the rate of CO2 immobilization as aqueous bicarbonate (solubility trapping) or as carbonate minerals (mineral trapping) in sandstone reservoirs depends upon reaction kinetics – but the relative fraction of each trapped CO2 species only depends upon the initial chemical composition of the host sandstone. For example, at the point of porosity occlusion the fraction of bicarbonate remaining in solution depends upon the initial Na and K content in the host rock but the fraction of carbonate mineralization depends only on the Ca, Mg, Fe content. Since ankerite is the dominant mineral that occludes porosity, the dissolved concentration of ferrous iron is also an important parameter. Finally, future efforts should focus on cross-comparisons and ground-truthing of simulations made for standard case studies as well as laboratory measurements of the reactivities of clay minerals.},
doi = {10.1016/j.apgeochem.2015.05.013},
journal = {Applied Geochemistry},
number = ,
volume = 61,
place = {United States},
year = {Wed May 27 00:00:00 EDT 2015},
month = {Wed May 27 00:00:00 EDT 2015}
}
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    Works referencing / citing this record:

    Compositional data analysis and geochemical modeling of CO2–water–rock interactions in three provinces of Korea
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