AGU Fall Meeting, December 11, 2013, San Francisco, USA

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MECHANISMS OF CO 2 INTERACTION WITH MONTMORILLONITE Background: Dynamic changes in geochemical and geomechanical properties of the natural reservoir seals utilized in the large-scale carbon

Vyacheslav Romanov, Evgeniy Myshakin, Bret Howard, George Guthrie This work combines experimental and theoretical studies on swelling clays that are commonly present in caprock, with regard to their

1 IR and XRD show that CO 2 can irreversibly intercalate within interlayer of smectite.

2 Rotation of clay layers induces rearrangement of interlayer ions, water, and carbon dioxide (in dry clays).

Future work: Theoretical studies on the role of cations in transition from CO 2 physical trapping to carbonation Experiments with a broader range of phyllosilicate materials CO 2 sorption isotherms:

1 MD simulations of the relative potential energy: mean X-Y compositions: X = number of water molecules, Y = number of CO 2 molecules per unit cell.

1 MECHANISMS OF CO 2 INTERACTION WITH MONTMORILLONITE Background: Dynamic changes in geochemical and geomechanical properties of the natural reservoir seals utilized in the large-scale carbon sequestration need to be accurately characterized to ensure safe long-term storage of carbon dioxide (CO 2 ). Vyacheslav Romanov, Evgeniy Myshakin, Bret Howard, George Guthrie This work combines experimental and theoretical studies on swelling clays that are commonly present in caprock, with regard to their geomechanical and geochemical integrity in the presence of CO 2. Summary: Smectites have high CO 2 sorption capacity compared to coal as measured by manometric apparatus. 1 IR and XRD show that CO 2 can irreversibly intercalate within interlayer of smectite. 1 DFT-based MD simulations attribute the red shift of IR-active asymmetricstretch vibrations of trapped CO 2 to elongation of the C-O bonds in the electric field of water molecules. 2 Rotation of clay layers induces rearrangement of interlayer ions, water, and carbon dioxide (in dry clays). The interlayer species follow the Moiré pattern created by the basal oxygens of clay phase. Future work: Theoretical studies on the role of cations in transition from CO 2 physical trapping to carbonation Experiments with a broader range of phyllosilicate materials CO 2 sorption isotherms: solid lines ( ) at 55 C; dotted lines ( ) at >9 C; dashed lines (---) for decompression (desorption). 1 MD simulations of the relative potential energy: mean X-Y compositions: X = number of water molecules, Y = number of CO 2 molecules per unit cell. IR carbonation: (a) IR of SWy-2 exposed in liqco 2 ( ) and scco 2 ( ); (b) difference, scco 2 liqco 2. 3 Intensity expt, SWy-2 MMT1 MMT4 MMT4_EXT5 clstr frequency, cm -1 XRD swelling: SWy-2 and STx-1b before and after exposure to sc- CO 2 and then after outgassing vs. references 1 : Na-SWy-2, Ca-SWy- 2, K-SWy-2, Ca-STx-1b, 1W, and 2W. CO 2 asymmetric stretch modes as observed experimentally (SWy-2) vs. simulated for MMT with 4 H 2 O and.5 CO 2 molecules per unit cell (MMT4), MMT with 1 water and.5 CO 2 molecules per unit cell (MMT1), MMT with 4 water and.5 CO 2 molecules per unit cell with interlayer distance increased by 5 Å (MMT4_EXT5), and a cluster of water and CO 2 molecule (clstr) using DFTbased BOMD simulations. 2 Clay/water/CO 2 system: red balls oxygen, purple sodium ion, white hydrogen, grey carbon. ROTATIONAL DISORDER OF TOT LAYERS: MOIRÉ PATTERNS The limiting value of the θ angle is 17.4 after which the rotational pattern disappears (the circles occupy 1/3 of the unit cell area) The d MP values are 99, 5, 33, and 25 Å for 3, 6, 9, and 12 rotational angles accordingly The ratio of the unit cell area and the circle area does not depend on the angle θ 2D density distribution maps: 6 θ, 6- and -2 compositions References: 1. Romanov, V.N. "Evidence of irreversible CO 2 intercalation in montmorillonite," Int. J. Greenhouse Gas Control 213, 14, and references therein. 2. Myshakin, E.M., Saidi, W.A., Romanov, V.N., Cygan, R.T., Jordan, K.D. "Molecular dynamics simulations of carbon dioxide intercalation in hydrated Namontmorillonite," J. Phys. Chem. C 213, 117, Hur, T.-B., Baltrus, J.P., Howard, B.H., Harbert, W.P., Romanov, V.N. "Carbonate formation in Wyoming montmorillonite under high pressure carbon dioxide," Int. J. Greenhouse Gas Control 213, 13, AGU Fall Meeting, December 11, 213, San Francisco, USA H 2 O CO 2

2 MECHANISMS OF CO2 INTERACTION WITH MONTMORILLONITE This work combines experimental and theoretical studies on swelling clays that are commonly present in caprock, with regard to their geomechanical and geochemical integrity in the presence of CO2. Sorption isotherms Smectites have high CO2 sorption capacity compared to coal as measured by manometric apparatus. Spectroscopy and microscopy IR and XRD show that CO2 can irreversibly intercalate within interlayer of smectite. MD simulations DFT-based MD simulations attribute the red shift of IRactive asymmetric-stretch vibrations of trapped CO2 to elongation of the C-O bonds in the electric field of water molecules.

3 Clay Intercalation Concept Molecular interactions in montmorillonite interlayer Al 3+ O(OH) 2 sheet w/charge deficiency silicate shee Mg 2+ silicate shee CO 2 sorption isotherms: solid lines ( ) at 55 C; dotted lines ( ) at >9 C; dashed lines (---) for decompression (desorption). Na + Ca 2+ H 2 O CO 2 Smectites have high CO 2 sorption capacity and hysteresis as measured by manometric apparatus. isomorphic substitutions IR and XRD show that CO 2 can irreversibly intercalate within interlayer of smectite. V. Romanov, Int. J. Greenhouse Gas Control (213) 14,

Methods and Techniques w/ preliminary results on mechanisms of CO 2 sorption isotherms Sorption-desorption hysteresis Magnitude corroborated by XPS CO 2 IR fingerprint interaction Dual-peak (unusual)

4 Methods and Techniques w/ preliminary results on mechanisms of CO 2 sorption isotherms Sorption-desorption hysteresis Magnitude corroborated by XPS CO 2 IR fingerprint interaction Dual-peak (unusual) red shift Rapidly converted to carbonates Sorption, mmol/g IR Intensity 1 SWy Pressure, MPa STx-1b SAz-2 Carbonates 142 cm cm -1 Intensity expt, SWy-2 MMT1 MMT4 MMT4_EXT5 clstr Wavenumber, cm -1 CO 2 asymmetric stretch modes as observed experimentally (SWy-2) vs. simulated for MMT with 4 H 2 O and.5 CO 2 molecules per unit cell (MMT4), MMT with 1 water and.5 CO 2 molecules per unit cell (MMT1), MMT with 4 water and.5 CO 2 molecules per unit cell with interlayer distance increased by 5 Å (MMT4_EXT5), and a cluster of water and CO 2 molecule (clstr) using DFT-based BOMD simulations frequency, cm -1 Romanov, V., Howard, B., Myshakin, E., Hur, T.-B., Baltrus, J. "CO2 Interaction with Swelling Clays," CCUS, May 213

5 Methods and Techniques w/ preliminary results on mechanisms of CO 2 sorption isotherms Sorption-desorption hysteresis Magnitude corroborated by XPS CO 2 IR fingerprint Dual-peak (unusual) red shift Rapidly converted to carbonates Simulated using ab initio Classical MD by Sandia differ XRD patterns of swelling interaction Reproduced at Univ. of Illinois (UIC) PNNL patterns are different Sorption, mmol/g IR Intensity 1 d-spacing, Å SWy Pressure, MPa W STx-1b SAz W Wavenumber, cm air CO₂ air SWy-2 NETL Carbonates 142 STx-1b cm 1476 NETL cm -1 Ca-SWy UIC Ca-STx PNNL J. Phys. Chem. C (213) 117, ; (212) 116, Int. J. Greenhouse Gas Control (213) 13, ; 14,

6 Rotational disorder of TOT layers: Moiré patterns

7 2D density distribution maps 6, 6- and -2 Rotation of clay compositions layers induces rearrangement of interlayer ions, water, and carbon dioxide (in dry clays). The interlayer species follow the Moiré pattern created by the basal oxygens of clay phase. H 2 O CO 2

8 MD simulations of the relative potential energy Mean X-Y compositions X = number of water molecules Y = number of CO2 molecules per unit cell

9 MD Summary Rotational disordering of hydrated montmorillonite clays is energetically demanding process. The largest energy increase occurs during the to 6 shift, then subsequent rotation proceeds with little potential energy hindrances. Rotation causes expansion of interlayer space by.1.2 Å depending on nature of the ions. Rotationally shifted dry montmorillonite systems are predicted to be lower in energy comparing to the zero degree case. Rotation is accompanied with decrease in d1-spacing by ~.1 Å. The process is explained in terms of favorable interactions of interlayer ions with the clay surfaces. Rotation of clay layers induces rearrangement of interlayer ions, water, and carbon dioxide (in dry clays). The interlayer species follows the Moiré pattern created by the basal oxygens of clay phase. Intercalation of carbon dioxide resulted in the following potential energy trend: rotational disordering requires energy for hydrated clays, while for dry clays the energy is lowering. Expansion of interlayer is computed for both clays during rotation and under CO2 load. The simulations show that CO2 invasion would not induce a bilayer formation in the 1W interlayer and carbon dioxide would tend to be coordinated at the external clay surface. CO2 is trapped in the 1W interlayer with limited solvation by water molecules. The calculated hydrogen bond lifetimes between CO2 and water is an order of magnitude smaller than lifetime values for water water, and water basal oxygens.

10 Contact Information Vyacheslav Romanov Evgeniy Myshakin

11 SUPPLEMENTAL MATERIALS I 2D density maps of carbon dioxide in dry Na-MMT at different rotation angles

12 SUPPLEMENTAL MATERIALS II Table 1. d 1 -spacing parameters for M-MMT systems computed at the degree of the rotational angle. ion This work DFT (vdw-ts) Expt. Na ± a 9.6 b ; 9.6 c Ca ± a 1. b ; 9.6 c K ± a 1. b ; 1. c a Voora, V.K.; Saidi, W. A., Jordan, K. D. J. Phys. Chem. A 115, 9695 (211) b Ferrage, E.; Lanson, B.; Sakharov, B. A.; Drits, V. A. Am. Mineral. 9, 1358 (25). c Abramova, E.; Lapides, I.; Yariv, S. J. Therm. Anal. Calorim. 9, 99 (27).

13 SUPPLEMENTAL MATERIALS III Calculated hydrogen bond lifetimes (τ, ps) for hydrated Ca- (in parentheses) and Na-MMT with and without intercalated CO 2 at various degrees of the rotational angle (..12 ) over 5 ns production run. Composition (X-Y) * 4- () 4- (3) 4- (6) 4- (9) 4- (12) τ H2O-clay τ H2O-H2O 13.5 (122.9) 97.5 (163.6) 86.5 (1.1) 66.2 (143.5) 78.9 (98.9) 63.1 (142.1) 76.3 (16.8) 59.6 (153.2) 76.7 (11.4) 62.9 (139.7) 6- () 6- (3) 6- (6) 6- (9) 6- (12) τ H2O-clay τ H2O-H2O 43. (59.9) 37.7 (53.) 41.5 (68.3) 36.7 (65.7) 4.3 (65.6) 36.4 (69.3) 42.5 (69.) 37.7 (68.5) 42.3 (61.2) 38.2 (65.8) 8- () 8- (3) 8- (6) 8- (9) 8- (12) τ H2O-clay τ H2O-H2O 38.5 (62.2) 2.5 (33.8) 4.7 (44.5) 2.9 (27.8) 38.3 (45.3) 21.6 (28.9) 37.1 (46.8) 21.1 (29.) 39.4 (48.1) 22.3 (26.3) 5-1 () 5-1 (3) 5-1 (6) 5-1 (9) 5-1 (12) 57.3 (47.8) 49.7 (47.) 47.3 (46.) 48.2 (45.6) 51.8 (46.9) τ H2O-clay τ H2O-H2O τ H2O-CO2 τ H2O-clay τ H2O-H2O τ H2O-CO (61.5) 6.2 (3.6) 38.1 (71.8) 4.6 (3.3) 39.9 (69.7) 4.5 (3.3) 41.5 (74.9) 4.5 (3.6) 45.8 (72.2) 4.1 (3.5) 5-2 () 5-2 (3) 5-2 (6) 5-2 (9) 5-2 (12) 61.6 (49.2) 49.7 (46.1) 52.3 (44.) 49.5 (47.6) 48.4 (46.7) 43.1 (63.7) 4.8 (2.4) 41.3 (69.5) 4.5 (2.6) 44.3 (73.4) 3.9 (3.) 42.2 (72.7) 3.6 (2.9) 41.8 (73.1) 4.3 (3.1)

ORIENTATION RELATIONSHIP OF TOT LAYERS cavity A unit cell of the Moiré pattern d MP is the distance between centers in the Moiré patterns; d a is the lattice

circles forming cavities The limiting value of the θ angle is 17.

14 ORIENTATION RELATIONSHIP OF TOT LAYERS cavity A unit cell of the Moiré pattern d MP is the distance between centers in the Moiré patterns; d a is the lattice parameter a, d IS is the radius within which the shifted ditrigonal rings are viewed as forming cavities; S MP is the area of one unit cell; S MP is the area of circles forming cavities The limiting value of the θ angle is 17.4 after which the rotational pattern disappears (the circles occupy 1/3 of the unit cell area) The d MP values are 99, 5, 33, and 25 Å for 3, 6, 9, and 12 rotational angles accordingly The ratio of the unit cell area and the circle area does not depend on the θ angle

COMPUTATIONAL DETAILS The stoichiometry is Na.75 Mg.75 Al 3.25 (OH) 4 (Si 4 O 1 ) 2 with a layer charge of.75 per O 2 (OH) 4 that is compensated by sodium or calcium ions.

15 COMPUTATIONAL DETAILS The stoichiometry is Na.75 Mg.75 Al 3.25 (OH) 4 (Si 4 O 1 ) 2 with a layer charge of.75 per O 2 (OH) 4 that is compensated by sodium or calcium ions. The 22x14x2 (18x1x2) supercell under PBC; total number of atoms in clay phase plus interlayer ions: (Na-MMT) and 1973 (Ca-MMT); with the largest interlayer H 2 O/CO 2 composition: 2984 (Na-MMT) and (Ca-MMT). NPT ensemble with Nose-Hoover thermostat / Parrinello-Rahman barostat and semi isotropic pressure coupling during 2 ns for production runs at T=34K, P=13MPa Ewald sums for electrostatics. The real part of the Coulombic potential was truncated at 11Ǻ. The Fourier part of the Ewald sums were evaluated by using the particle mesh Ewald (PME) method.

COMPUTATIONAL DETAILS (cont.) Classical force fields used: Clayff plus flexible SPC:[R. Cygan, J.-J. Liang, A. Kalinichev, J. Phys. Chem. B, 18, 1255 (24)] Flexible CO 2 force field: [R. Cygan, V.

16 COMPUTATIONAL DETAILS (cont.) Classical force fields used: Clayff plus flexible SPC:[R. Cygan, J.-J. Liang, A. Kalinichev, J. Phys. Chem. B, 18, 1255 (24)] Flexible CO 2 force field: [R. Cygan, V. Romanov, E. Myshakin, J. Phys. Chem. C, 116, 1379 (212)] Potential energy of rotated clay systems: 1) Position constrains: 2) Enforced rotation: Ω(t) is a matrix describing rotation around an axis; ω i is an optional mass-weighted pre-factor; x c, y c are positions of the center of mass. [C. Kutzner, J. Czub, H. Grubmuller, J. Chem. Theory Comp. 7,1381 (211)]

17 RELATIVE POTENTIAL ENERGY AND d 1 -SPACING 2 6- Na + 6- Ca Na + 6- Ca E, kj/mol Na + - Ca 2+ - K Na Ca 2+ d 1 -spacing, Å Na + - Ca 2+ - K Na Ca Na + -2 Ca Na + -2 Ca angle, degree angle, degree

18 DENSITY DISTRIBUTION OF INTERLAYER IONS a) Na+ density, kg/m b) Na D Na + density distribution map in dry montmorillonite interlayer distance, Å at 6 degrees of the rotational angle 1D density profile of Na + in a) dry montmorillonite and b) hydrated 1W montmorillonite and as a function of the rotational angle

19 ELECTROSTATIC AND LENNARD-JONES CONTRIBUTIONS E, kj/mol PotEtot SR_EL rec_el SR_LJ sum a) b) E, kj/mol Ca-MMT PotEn PYRO PotEn Ca-MMT Elec. PYRO Elec angle, degree Calculated contributions into relative potential energy for 6- (upper) and - (lower) compositions in Ca-MMT as a function of the rotation angle Ca-Ca, Ca-O, Ca-Si: Ca-MMT O-O, Si-Si, O-Si: Ca-MMT O-O, Si-Si, O-Si: PYRO angle, degree Comparison of potential energy, electrostatics (upper) and electrostatic atomic pair-wise contributions (lower) for dry Ca-montmorillonte and pyrophyllite

20 DENSITY DISTRIBUTION OF WATER MOLECULES in Na-MONTMORILLONITE density, kg/m H2O interlayer distance, Å 1D density profile of water molecules in hydrated (1W) Na-montmorillonite for the 6- composition in the interlayer. 2D water density distribution map in Na-montmorillonite for the 6- composition at 6 degrees of the rotational angle

21 DENSITY DISTRIBUTIONS OF CO2 AND IONS in DRY Na-MONTMORILLONITE density, kg/m a) CO a) Na+ density, kg/m interlayer distance, Å 1D density profile of CO2 (upper) and Na+ (lower) in dry (W) Na-MMT for the -2 composition in the interlayer. 2D CO2 density distribution map in Na-MMT for the -2 composition at 6 degrees of the rotational angle

22 SWELLING BEHAVIOR OF HYDRATED Na-MONTMORILLONITE UPON CO 2 INTERCALATION d 1 -spacing (Å) number of water / unit cell d 1 -spacing as a function of number of water molecules at fixed numbers of CO 2 molecules per unit cell. Dashed lines indicate ranges of basal d 1 -spacing corresponding to 1W and 2W hydration states. [Myshakin, E.M.; Saidi, W. A.; Romanov, V. N.; Cygan, R. T.; Jordan, K. D. J. Phys. Chem. C, 117, 1128 (213)]

23 DENSITY DISTRIBUTIONS OF CO2 in HYDRATED Na-MONTMORILLONITE density, kg/m CO interlayer distance, Å 1D density profile of CO2 in hydrated (1W) Na-montmorillonite for the 5-2 composition in the interlayer. 2D water density distribution map in Na-montmorillonite for the 5-2 composition at 6 degrees of the rotational angle

24 DENSITY DISTRIBUTIONS OF WATER MOLECULES in Na-MONTMORILLONITE WITH INTERCALATED CO2 density, kg/m H2O interlayer distance, nm 1D density profile of water molecules in hydrated (1W) Na-montmorillonite for the 5-2 composition in the interlayer. 2D water density distribution map in Na-montmorillonite for the 5-2 composition at 6 degrees of the rotational angle

25 Clay/Coal Abundance Map Excess sorption, mmol/g o C 95 o C 15 o C CO 2 pressure, MPa STx-1b fast ar SWy-2 fast ar STx-1b fast dry SWy-2 fast dry CO 2 INTERACTION WITH GEOMATERIALS Romanov et al, Environmental Science & Technology (29)

26 IR Experiments vs MD Simulations (cm -1 CO ) CO 2 +air CO 2 +HF 2 (8 mos.) (25 o C) Ca-rich Na-rich Positions of asymmetric stretch in acid-digested montmorillonite samples are consistent with literature data for halide-co 2 anions The magnitude of the peaks has not changed after boiling in HF Surprisingly, asymmetric stretch is red-shifted contrary to DFT and ab initio computations for alkali-co 2 cations CO 2 INTERACTION WITH GEOMATERIALS

27 Asymmetric stretch Prior to background subtraction Same as 1 but 8 months later (5x) "CO 2 INTERACTION WITH GEOMATERIALS"

28 Vibrational modes It was observed that the stretch peak attributed to intercalation appeared after exposure not only to high pressure but also to high temperature. Experimentally, no IR (diffuse reflectance) bending mode of CO 2 was detected in excess of background (degassing) after exposure of clay samples to various temperature and pressure cycles. Bend mode is expected to blue-shift 6 7 CO 2 bending mode (R. Cygan,/SNL 21) Romanov et al, "CO 2 interactions with swelling clays (TMC, Spain, 21)

29 Swelling behavior of SWy-2 3 Na 3 (Si 31 Al)(Al 14 Mg 2 )O 8 (OH) 16 nh 2 O (1) d-spacing (Å) unit cell basis Synchrotron XRD: as 24C Synchrotron XRD: a.r. + CO 8C Experimental Fu et al. (199) MD Simulation M H2 O / M clay MD Simulation (R. Cygan,/SNL 21) "CO 2 INTERACTION WITH GEOMATERIALS"

Multiphase Monte Carlo and Molecular Dynamics Simulations of

Multiphase Monte Carlo and Molecular Dynamics Simulations of Water and CO 2 Intercalation in Montmorillonite and Beidellite Meysam Makaremi, 1,2,3 Kenneth D. Jordan, 1,2 George D. Guthrie, 1,** and Evgeniy