IN SITU 13 C NMR TO DEVELOP MATERIALS FOR THE CAPTURE AND SEQUESTRATION OF CO 2 Sophia Hayes, Mark Conradi, Phil Skemer Washington University in St. Louis
Carbon Sequestration Sequestration conditions: 50-100 atm 50-120 C Image from http://www.personal.psu.edu/afr3/blogs/siow/co2-sequestration.jpg
Overview High-pressure, high-temperature NMR requires specialized, noncommercial probes. (NMR of gases, liquids, solids simultaneously). Can be applied to batch reactors or small-scale versions of CO 2 -subterranean processes Collaborators: Prof. Mark Conradi, Physics Prof. Phil Skemer, Earth & Planetary Science Researchers: Andy Surface Jeremy Moore Funding: WU Consortium for Clean Coal Utilization
Project Goals Determine chemical conditions that lead to CO 2 capture and mineralization. Learn to identify CO 2 phase and density from NMR, including dissolved CO 2 and other forms (i.d., carbonic acid, carbonate, etc.). Create a Center for spectroscopy and imaging of CO 2 at WU: rock samples (for sequestration) solid-phase adsorbents (for capture) chemical feedstocks (for utilization)
NMR: a One-slide Introduction NMR = nuclear magnetic resonance An element-selective, non-destructive form of spectroscopy that examines nuclear spins of specific isotopes, such as 13 C, 1 H, 15 N, 14 N Solution-state and gas-phase NMR narrow lines 1000 800 600 400 200 0-200 -400-600 -800-1000 ppm Solid-state NMR subject to multiple broadening interactions. 1000 800 600 400 200 0-200 -400-600 -800-1000 ppm
NMR hardware development 6 High Pressure CO 2 NMR Magnet NMR Probe Heater
Physical Processes Neat CO 2 NMR can identify and separate signals from gas, liquid, supercritical CO 2. Most envisioned sequestration is at hightemperature, highpressure. Goal: learn to identify CO 2 phase and density from NMR, for later use in rock measurements.
Speciation: What form is the 13 C (1) (2) (3) (4) H 2 O + CO 2 H 2 CO 3 H + + HCO 3 2H + + CO 3 2 NMR frequencies of (1), (2), (3), (4) are different. NMR intensities yield concentrations of each. NMR is an in situ ph meter. Figure is from in vivo 13 C MRI, showing CO 2 peak and HCO 3 peak M.A. Schroeder et al., Cardiovascular Research (2010) 86,
In Situ Monitoring of a Reaction 9 13 C NMR of heterogeneous mixtures Mg(OH) 2, CO 2, water 13 C NMR Surface et. al, Environ. Sci. Technol. 2012 DOI: 10.1021/es301287n 90.6 atm, 80 C 40 min
In Situ Monitoring of a Reaction 10 13 C NMR Surface et. al, Environ. Sci. Technol. 2012. DOI: 10.1021/es301287n 80 bar, 80 C 58 hrs rxn
In Situ Monitoring of a Reaction 11 13 C NMR 13 C NMR 81 C, 80 bar ~1.5 weeks sc-co 2 CO 2(aq) HCO 3 (aq) Solid Carbonate
Numerous Magnesium Carbonate- Related Minerals 12
Hydromagnesite CONFIDENTIAL PLEASE DO NOT CITE NOR DISTRIBUTE [4MgCO 3 Mg(OH) 2 4H 2 O]
Magnesite MgCO3
Solid Lineshape Indicative of Structure 15 Simulation Our Product(s) Pure MgCO 3 Data Fit
Conclusions Developed a new in situ NMR tool that: Distinguishes between 13 C NMR of gas, liquid and supercritical CO 2 phases. Monitors carbonate formation in mineral reactions with CO 2 for a variety of conditions (i.e., temperature, pressure, ph, and brine composition.) Measures ph with accuracy (+/- 0.1 ph) at high pressures and temperatures. Able to analyze heterogeneous mixtures, candidate rocks for geosequestration, or other chemicals for in situ reactions. Carbonates yield characteristic lineshapes and chemical shifts that allow their local site symmetry (structure) to be elucidated. Mineral phases: nesquehonite, hydromagnesite, dypingite identified This spectroscopic tool enables quantification and identification of carbonates in complex mixtures. Reaction conditions favorable to their formation can be studied, as well as the rates of these reactions for optimization of CO 2 utilization and sequestration.
References and Future Funding Giammar, Daniel E.*; Wang, Fei; Guo, Bin; Surface, J. Andrew; Peters, Catherine A.; Conradi, Mark S.; Hayes, Sophia E. Impacts of Diffusive Transport on Carbonate Mineral Formation from Magnesium Silicate-CO 2 -Water Reactions submitted Envi. Sci Tech. 2014. Moore, Jeremy K.; Surface, J. Andrew; Brenner, Allison; Louis, Wang; Skemer, Philip; Conradi, Mark S.; *Hayes, Sophia E. Quantitative Identification of Metastable Magnesium Carbonate Minerals by Solid-State 13 C NMR Spectroscopy submitted Envir. Sci. Tech. 2014. Surface, J. Andrew; Wang, Fei; Zhu, Yanzhe; Conradi, Mark; Hayes, Sophia E.; *Giammar, Daniel E. Measuring ph at high pressure and temperature using 13 C NMR Envir. Sci. Tech., submitted 2014. Under revision Surface, J. Andrew; Skemer, Philip ; *Hayes, Sophia E.; *Conradi, Mark S. In Situ Measurement of Magnesium Carbonate Formation from CO 2 Using Static High Pressure and Temperature 13 C NMR Envir. Sci. Tech., 2013, 47, 119 125. doi: 10.1021/es301287n Future Funding DOE National Energy Technology Lab, DE-FOA-0001010 Impact of microstructure on the containment and migration of CO2 in fractured basalts (Lead-PI: Dan Giammar; Co-PI s: Mark Coradi, Sophia Hayes, Phil Skemer, and Brian Ellis, Univ MI)
Carbon Capture Materials Solid-state 13 C NMR of materials for adsorption of CO 2, dominantly in flue gases Prof. Chris Jones Georgia Institute of Technology Prof. Michael Guiver Univ. of British Columbia
Solid Amine Sorbents Class 1: Polyethyleneimine (PEI) Polymer physically impregnated into porous silica support Class 3: Hyperbranched Aminosilica (HAS) In situ polymerization of amine monomers on porous silica support Solid amine sorbents adsorb CO 2 : By chemisorption? By physisorption? Bollini, Didas, Jones, J. Mater. Chem., 2011, 21, 15100-15120
ppm CONFIDENTIAL PLEASE DO NOT CITE NOR DISTRIBUTE In Situ Static 13 C NMR: PEI NMR exhibits both broad and narrow features 13 C NMR of solids and gases Solid signal found at different chemical shift Chemisorption CO 2 gas peak confirmed by evacuation Broad peak from solid reaction product 300 250 200 150 100 50 0
CONFIDENTIAL PLEASE DO NOT CITE NOR DISTRIBUTE Ex Situ Cross-Polarization Magic Angle Spinning NMR Rapidly rotating the sample narrows the line width of resonances from solids. (Ex situ experiments) Narrowed lines enables peak identification based on their (familiar) chemical shifts In Situ 13 C static NMR of reaction mixture (gas and solids) Ex Situ 13 C CPMAS of solids collected from in situ probe Solid adsorption product (163.2 ppm) * * PEI polymer 47.7 ppm 38.3 ppm 300 250 200 150 100 50 0 ppm (No CO 2 gas) * * 300 250 200 150 100 50 0 ppm * * 300 250 200 150 100 50 0 ppm
CONFIDENTIAL PLEASE DO NOT CITE NOR DISTRIBUTE Solid Adsorption Product What are the possible products? (~164 ppm) (~163 ppm) (~165 ppm) urea carbamate bicarbonate
CONFIDENTIAL PLEASE DO NOT CITE NOR DISTRIBUTE Solid Adsorption Product What are the possible products? Carbamate (~164 ppm) Bicarbonate (~163 ppm) Urea (~165 ppm)
CONFIDENTIAL PLEASE DO NOT CITE NOR DISTRIBUTE Solid Adsorption Product What are the possible products? (~164 ppm) (~163 ppm) carbamate bicarbonate
CONFIDENTIAL PLEASE DO NOT CITE NOR DISTRIBUTE Conclusions Physisorbed CO 2 observed with in situ 13 C NMR when the overpressure of CO 2 is still on the sample Chemisorbed species are a broad resonance typical for disordered carbons, mixtures, and in the vicinity of protons ( 1 H spins). Ex situ 13 C CPMAS spectra, shows the chemisorbed species to be bicarbonate and carbamate in a mixture. The combination of in situ and ex situ NMR will enable new materials to be developed for enhanced CO 2 capture. Once again, the ability of NMR to quantify and identify species in mixtures enables reaction pathways to be studied and optimized.
References and Future Funding Moore, Jeremy; Sakwa-Novak M.; Chaikittisilp, W.; Conradi, M.; Jones, C.; *Hayes, S. CO 2 Adsorption Products in Supported Hyperbranched Aminosilica Adsorbents Utilizing 13 C Solid-state NMR and In Situ Spectroscopy, draft in preparation Moore, Jeremy; Guiver, Michael; Du, Naiying; Hayes, Sophia E.; *Conradi, Mark S. Molecular motion of adsorbed CO 2 on a tetrazole-functionalized PIM polymer studied with 13 C NMR J. Phys Chem C. 2013,. 117, 22995-22999. doi: 10.1021/jp4084234 Funding DOE Energy Frontiers Research Center, DE-FOA-0001010 Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (Lead PI: Krista Walton, GATech, Hayes is Sr. Personnel) NSF CBET (1403239) Collaborative Research: In-situ Molecular Spectroscopy of CO 2 Adsorption/Desorption Processes on Supported Amine Adsorbents (Co-PIs Chris Jones, GATech; Sophia Hayes, WU)