FIRST PRINCIPLES STUDIES OF MINERAL CARBONATION REACTION PROCESSES IN SERPENTINE MINERALS

Andrew V.G. Chizmeshya,*° Michael J. McKelvy,*° Deirdre Gormley,° and G.H. Wolf +
*Center for Solid State Science, °Science and Engineering of Materials Graduate Program and +Department of Chemistry and Biochemistry; Arizona State University; Tempe, AZ 85287 U.S.A.

Research Center (ARC), Arizona State University (ASU), has been achieved in under an hour (~150oC and 115- closely integrating our studies with those being SIMULATION AND MODELING GOALS COMPUTATIONAL METHODS mented within the GAMESS package), and the non- we have undertaken simulations of both the bulk and
INTRODUCTION
Los Alamos National Laboratory, the National Energy 185 atm CO2) using an aqueous reaction process simultaneously performed at the Albany Research Center, empirical VIB DFT method. near-surface regions. In the latter case, 720oC simulations
The potential environmental effects of increasing Technology Laboratory, Pennsylvania State University, developed at the U.S. DOE Albany Research Center1. and in a joint ASU-Argonne National Laboratory (ANL) § Understanding the enhanced carbonation reactivity of Most of our simulations employ an efficient quantum reveal that “silica-layer” hydroxyl protons have very high
atmospheric CO2 levels are of major worldwide concern. study that focuses on in situ investigations of aqueous- CONCLUSIONS
University of Utah and Science Applications International Unfortunately, heat pretreatment is energy intensive and heat pretreated serpentine: What is the dehydroxylation mechanical description based on density functional theory diffusivities, but kinetics limit the formation of water.
One alternative for managing CO2 emissions is carbon Corporation. costly. An atomic-level understanding of the mechanism(s) solution serpentine carbonation reaction mechanisms. mechanism? Can first-principles modeling help (DFT), which provides access to all the measurable We have shown that modern first-principles electronic Instead, meta-stable water is observed to form in the
sequestration: the capture and secure confinement of CO2 Mg-rich lamellar hydroxide minerals, such as by which heat pretreatment enhances serpentine Key focal points of our multi-year project include: interpret XPD and IR spectra? quantities derivable from the knowledge of the ground structure simulations are able to accurately describe the “brucite-like” layers within the bulk crystal.
before it is emitted to the atmosphere. Successful serpentines, represent a promising class of feedstock carbonation reactivity is therefore crucial to being able to (i) simulation of the structural/compositional changes state wave function of a system, including the electronic structural, elastic and vibrational properties of magnesium This is likely a key step in the initial dehydroxylation
technologies must be environmentally benign, permanent, materials, with good potential for economically viable engineer more cost-effective pretreatment processes. associated with serpentine heat-activation to understand § Fundamental simulations of mineral surface and vibrational spectrum of the subject material, and its bearing feedstock minerals. Using these same methods, process associated with heat activation. In both surface
economically viable, safe and effective. As a result, their process development. The key reaction for serpentine is: Many important factors that govern serpentine heat- their role in enhancing carbonation reactivity, (ii) reconstructions during dehydroxylation à impact compressibility/elasticity. In addition, microscopic simulations of the initial stages of 1T-Lizardite and bulk regions, the silica layers exhibit long-term
timely development represents a significant challenge. activation via dehydroxylation are only observable at the development of a non-empirical site reactivity model for on dissolution rates, and near-surface mineral quantities not normally accessible in the laboratory are dehydroxylation reveal that the process involving a dynamic stability and may be implicated in the stability
Unlike many other proposed CO2 sequestration Mg3Si2O5(OH)4 + 3 CO2 → MgCO3 + 2 SiO2 + 2 H2O + 64 kJ/mol atomic level. CO2 with serpentine, (iii) detailed investigation of mineral carbonation mechanisms. available including atomic forces, local electric potentials brucite-layer hydroxyl, and a cage proton from an adjacent of the highly reactive amorphous meta-serpentine.
technologies, which provide storage, CO2 mineral surface dissolution mechanisms that govern carbonation and fields – useful fictitious constraints may also be layer, represents the lowest energy reaction path2. Dynamical simulations of bulk H2O-CO2 solutions were
sequestration provides permanent disposal via OBJECTIVE kinetics, and (iv) simulation of Infrared/Raman, EELS,
The carbonation of unpretreated serpentine is found to be § The role of substitutional impurities (e.g., Al, Fe): imposed (artificial masses, artificial charges, stationary Simulations of moderately dehydroxylated systems also found to be accurate. Future work will focus on the
geologically stable mineral carbonates (e.g., MgCO3). As significantly slower than that observed for olivine, The objective of this project is to use advanced first- XPD, and XANES spectra to help interpret experimental Impact on carbonation? ions). In addition to our own computer codes, we make containing 50% residual hydroxyl, corresponding to mineral solution interface. --------------------------------
such, mineral sequestration provides permanent another Mg-rich feedstock mineral currently being principles simulation techniques in concert with findings. use of the WIEN2K and CRYSTAL98 packages for all- Mg3Si2O6(OH)2, show that experimentally observed x-ray
containment and avoids many adverse environmental actively explored. However, serpentine is much more experimental observations to develop a detailed, § Simulations of carbonation processes and speciation of electron calculations, and the VASP and DMol3 codes for features are due to H2O being preferentially removed from ACKNOWLEDGEMENTS
Schematic illustration of the
consequences and the cost of continuous site monitoring. plentiful in readily mineable deposits worldwide, making quantitative, atomic-level understanding of aqueous- synergy between the sampling carbon-bearing species in aqueous solutions. molecular dynamic and thermodynamic calculations of the alternating lizardite layers with a ratio of 4:1, or greater. This work is supported by DOE Fossil Energy
The major remaining challenge for CO2 mineral it the CO2 sequestration feedstock material of choice if its solution serpentine carbonation mechanisms. The goal is volume sensitivity and range gas, crystalline and liquid states. We also make use of This results in an open structure, with potentially Advanced Research (National Energy Technology
sequestration is economically viable process carbonation reactivity can be further enhanced. When to develop the necessary atomic-level understanding to of the proposed modeling approximate methods to treat systems too large or
§ Ab initio simulations of electron energy loss spectra enhanced dissolution potential and higher carbonation Laboratory) UCR Grants DE-FG26-98FT40112, DE-FG26
studies herein and dynamic
development. This is the focus of the CO2 Mineral serpentine is heat pretreated for an hour or more at over facilitate the engineering of improved carbonation high-resolution transmission (EELS), x-ray powder diffraction spectra and complex to be tractable using ab initio methods. Examples reactivity, as observed experimentally. -01NT41295, and DE-FG26-01NT41282 and NETL/ANL
Sequestration Working Group managed by DOE Fossil 600oC, its carbonation rate has been found to increase feedstock materials and reaction processes for CO2 electron microscopy vibrational spectra. of such tools also include semiempirical quantum- Large scale molecular dynamics simulations of micron Contract 1F-01262. We thank Dr. H. Bearat for FESEM
Energy, which includes members from the Albany dramatically (see below). 70-85% carbonate conversion sequestration. Scientific productivity is optimized by (DHRTEM) mechanical methods such as PM3 and AM1 (as imple- scale systems is prohitive. To circumvent this limitation images and Dr. R. Sharma for EELS analysis.

BASIC REACTANT/PRODUCT PROPERTIES: EFFECTS OF HEAT-TREATMENT: QUANTUM MOLECULAR DYNAMICS SIMULATIONS:

Serpentine Minerals with Ideal “Fingerprinting” via Electron Energy Loss Spectra (EELS): Controlled Intermediate Formation -- Enhanced Carbonation Mineral Reactant Decomposition: Bulk and Surface Stability
Composition Mg3Si2O5(OH)4 Local probe of oxygen environment à interpretation of
structural/chemical alteration of feedstock during processing Objectives: Simulation Conditions:
Lizarditeà platy CR
YS • Use state-of-the-art quantum simulation to study the • 72 to 144-atom cells (as in earlier dehydroxylation calculations).
300 nm 1T-lizardite: % OH Tactivation TA
LL dynamics of protons/hydroxyls as a function of temperature. • 1.5 femtosecond timestep integration using the Verlet algorithm
Heat Activation at 720oC
IN
Interpretation: E
AMO
RPH
OUS • Diffusion of H, OH, H2O – stability of silica sheets. • Local density approximation (LDA)
Mechanisms:
• Ultra-soft pseudopotentials used to replace core electrons.
Shoulder feature at edge onset ~ 5 eV • Electronic structure computed (using the VASP code) at every
se • Significant proton diffusion found for
due to silica cage hydroxyl oxygen. ha time step + velocity rescaling.
a-p
protons in “cage” sites (e.g., within
105 oC

Prominent feature at 15 eV due to silica sheet).

Mg near neighbor oxygens (Apecal 100 oC

tetrahedral oxygens and “brucite-like” • Frequent formation of meta-stable

hydroxyl oxygens).
125 oC
XPD
A visual guide to the characteristic features Results of a multi-phase analysis of the XPD Bulk lizardite @ 720oC water within brucite layers in the
Field Emission 120 oC
exhibited by meta-serpentines. The low angle spectra as a function of degree of de-
Scanning Electron Main contribution to feature at ~22 eV Above: “Philips mine” lizardite is heat-treated in a bulk crystal. Diffusion rate reduced
feature (2q~6o) is labeled as a-phase and is hydroxylation. Note the coincidence of the near the surface.
(1010) (1120) Microscope due to apecal tetrahedral oxygen. TGA and quenched at the temperatures indicated
treated as distinct in the phase analysis phase fractions of amorphous and a-phase
Images of Globe-A Energy Loss Near Edge Spectra obtained using by dots to produce a range of reactant materials
shown at right. The broad “glassy” feature below 25%. The most efficient carbonation is
mine serpentine (meta-serpentines) with varying OH content. • Silica layers remain integral on a long
Antigoriteàmodulated feedstock showing
the FPLAPW method within the generalized 34 eV feature mainly related to brucite 185 oC
centered around 2q ~30o, which grows in observed near the point where the green and
gradient approximation(GGA). Full dynamic form
Lizardite (platy) layer hydroxyls. for residual hydroxyl contents < 50%, red curves cross (~ 11% residual hydroxyl). time scale compared to the proton
factors were computed using crystalline Bloch Right: Progression of XPD spectra illustrating the
and Chrysotile states. A broadening of ~ 2eV was applied to the evolution of structure over the composition range
is associated with enhanced carbonation (left). Preferred orientation not included… hopping rate between cage sites.
(fibrous) components. raw spectra to simulate experimental data. shown in the left margin. The colored dots indicate
CARBONATION:
none trace strong
Bulk lizardite @ 20oC
the degree of carbonation achieved at the • High quality static • Study will yield diffusion constants for
Carbonate product: …evolution of carbon K-edge temperatures shown. lattice calculations à water, protons and magnesium as a
Room temperature Lizardite (~20oC): What is the real feedstock structure?
C K-edges 4
Primitive unit cell: function of temperature (underway).
C K-edges
50000

• New, slightly metastable ( b ) phase predicted at room temperature.

Correlation between Infrared spectroscopic Microscopic model of 50% meta-lizardite from first principles:
45000
40000
MgCO3 Reference
Chrysotile à coiled lizardite a = 5.265 Å c = 7.090 Å
3
MgCO3
• Inverted hydroxyl within the brucite layer
ELNES Intensity
ELNES Intensity

35000

features and character of XPD. Lizardite Free surface (1120)

30000
25000

• Origin for unexplained splittings and asymmetry of various

2
20000

600 nm
@ 720oC
2-
"Carbonated" Samples
Interpretation: b-lizardite a = 5.344 Å c = 7.092 Å
15000
CO3
(in situ DHRTEM)
in-plane features? e.g. (100) and (101)?
10000
1
5000
0
-5000 CO2 • Origin of the unexplained high frequency shoulder on the OH
DE = 0.021 eV/atom
0

The meta-serpentine inter-

-10000

280 300 320 340

Energy Loss (eV)
360 -10 0 10 20 30
Energy Loss (eV)
40 50
bands. Calculations in progress.
mediates formed include a range (n.b. kBT ~ 0.025eV at 300oK)
calculated of amorphous solid-solution
and/or locally-ordered material(s)
and a stage-2 phase with ~14.6 Å Aqueous System: Speciation in the
Comparison of simulated structure Construct several dozen 144-atom lizardite cells and
FUTURE WORK:
n pH
Solid Reactants: Forsterite, Olivine, Lizardite, Meta-lizardite remove (via hetero- or homo- planar removal) 50% water interatomic order. They form and ARC (Ref.1)
properties with experiment: Solid Products: Magnetite, “carbonate” (Mgx,Fe1-x)CO3, silica, others? à 8·Mg3Si2O5(OH)4 - 8·H2O transform on heating, retaining - Speciation and diffusivity carbonation reaction
Validation of predictive capability residual OH levels from ³ 12 to information for aqueous solution (1 M NaCl, CO2(aq)
n Finding: Low-angle (~6o) XRD feature can only be 0.64 M NaHCO3)
HCO3–
Dissolution rate estimates from simulation: dependence on surface orientation and
reproduced when hydroxyls preferentially dissociate from
1% after complete lizardite/ species is very limited.
alternating layers with a ratio of 4:1 or greater. serpentine decomposition. based on empirical CO32– impurity concentration (extension to olivine).
- The thermodynamics of the equilibrium
CO2-H2O system in the Application of first-principles COSMO-RS (Conductor like screening model for
“Silent”

OH–
50% dehydroxylated material exhibits new constants and
The OH groups in meta-
feature at 2q~ 6o while parent phase features presence of solutes is complex known activities. real solvents) to solution speciation.
are still present. serpentine derived from lizardite (many key parameters unknown).
with a minor chrysotile component
Low angle feature still present in ~10% Full first-principles quantum molecular dynamics simulations of the mineral-solution
Origin of lizardite vibrational bands (e.g., Globe-A mine feedstock)
dehydroxylated material, but with remnants of
primarily “in-plane” reflections remaining from in the hydroxyl stretch frequency have a new structural Validation of quantum molecular dynamics simulations for liquid phases: interface.
the parent phase. range. Low frequency feature environment unlike the parent
(~3640 cm-1) is associated with Timescales: ~ ps
The appearance of two new frequencies in the
~10% OH meta-serpentine suggests that the
brucite layer hydroxyl motion.
Results obtained quantum lattice First principles
serpentine or the lizardite derived
meta-serpentine (see Infrared Length scales: ~ nm REFERENCES:
local hydroxide environment has changed. simulation of 50% Spectroscopy panel). Such
dynamics using a plane wave 10 ps run at STP: 1) W.K. O’Conner, R.P. Walters, D.C. Dahlin, G.E.Rush, D.N. Nilsen and P.C. Turner, Proc. 26th Int. Tech. Conf.
pseudopotential approach. Note meta-lizardite structure related frequency shifts
New vibrational signature near ~ 3740 cm-1 . are not observed in meta- On Coal Util. & Fuel Sys., p. 765-716 (2001).
How is it related to the structure of meta- the excellent agreement with showing a staged <|ri(t)-ri(0)|2> = 6Dt
serpentine? Simulations suggest the formation experiment (left). partial disorder of the magnesium sub-lattice resulting in the serpentines derived from pure 2) Andrew V.G. Chizmeshya, Otto F. Sankey, Michael J. McKelvy, R. Sharma, R.W. Carpenter, George Wolf,
of siloxane intermediates (Si-OH groups) upon a-phase feature at 2q~6o. Silica sheets remain rigid, and few lizardite (e.g., Philips mine D ~ 2.9 x 10-5 cm2/s Hamdallah Bearat and Jason Diefenbacher, , Proc. 27th Int. Tech. Conf. On Coal Util. & Fuel Sys., p. 803-814 (2002).
decomposition. Predicted frequencies are in the hydroxyls are required to “prop” up the structure. Enhanced Serpentine feedstock).
range 3700-3770 cm-1 depending on Si Initial (a) and final (b) states of liquid Total radial distribution (Dexp ~ 2.5 x 10-5 cm2/s) 3) Michael J. McKelvy, R. Sharma, R.W. Carpenter, George Wolf, Andrew V.G. Chizmeshya, Hamdallah Bearat
termination. access to Mg may explain increased dissolution/carbonation simulated H2O at STP. Dashed lines function and Jason Diefenbacher, Proc. 27th Int. Tech. Conf. On Coal Util. And Fuel Syst, Vol.1, 791-802 (2002).
reactivity. indicate hydrogen bonding.