CO 2 Capture using Nanoparticle-based Ionic Materials (NIMs) - PowerPoint PPT Presentation

CO 2 Capture using Nanoparticle-based Ionic Materials (NIMs) Ah-Hyung Alissa Park Earth and Environmental Engineering & Chemical Engineering Lenfest Center for Sustainable Energy Columbia University Sustainable Fuels from CO 2 , H 2 O and Carbon-Free Energy May 4 th , 2010

Projected Global Energy Demand & Supply The world energy demand is projected to increase by over 40% in the next two decades Fossil Fuels will remain the dominant source

Coal-fired Power Plants

Our Research Goals Use domestic energy Wind , Fossil Gasoline Gasoline sources to achieve Hydro energy independence Heat Heat Diesel Diesel Geo Refining with environmental Nuclear sustainability Jet Fuel Jet Fuel Electricity Electricity Synthesis Solar Solar Gas CO 2 Ethanol Ethanol Nuclear Biomass Carbon Methanol Use carbon neutral energy Chemicals Chemicals Wind , sources such as biomass & Fossil DME DME Hydro MSW Hydrogen Hydrogen Biomass Geo Municipal Municipal Solid Solid Integrate carbon capture and Wastes Wastes storage (CCS) technologies into CCS the energy conversion systems

Gasification-Based Energy Production System Concepts Sulfur r By By-Pro Product Fly A y Ash By By-Pro Product Slag ag By By-Pro Product Steigel and Ramezan, 2006

Petroleum-based vs. Synthetic Liquid Fuels $81.81 80 (04/28/10) 70 Steynberg, (2006) 60 Crude oil prices once Crude Oil Price ($/Barrel) again at 1973 levels 50 40 30 20 10 0 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 US$ of the day (Nominal) 2003 US$ (Real)

Carbon Dioxide Sequestration Options CO 2 Removal Separation Transportation Sequestration • Necessary Characteristics - Capacity and price - Environmentally benign fate - Stability

Carbon Capture Schemes • From concentrated sources vs. diffuse sources • Integrated Carbon Capture Technologies Source: NETL, 2008

Carbon Capture Typical Amine Scrubbing Process • Most widely employed CO 2 capture method is using • Concerns with Amine Scrubbing Technology 1.High parasitic energy penalty (Goff et al., Ind. Eng. Chem. Res. 2004) 2.High cost - capital and operating 3.Corrosion & degradation (due to SO 2 , O 2 , particulate, etc) 4.High vapor pressure leads to fugitive emissions 10

Carbon Capture Schemes • From concentrated sources vs. diffuse sources • Integrated Carbon Capture Technologies Source: NETL, 2008

What is NIMS? Nanoparticle Ionic Materials A Nanoscale Analogue to Ionic Liquids + = Nanoparticle Ionic Corona NIMS advantages • Zero Vapor Pressure • >600 counter ions affiliated with a single nanoparticle (unlike ionic liquids where each ion is the source of a single bearing CO 2 capture site) • Ionic coronas forming the Canopy are forced to distort their natural conformations to fill in the space between the cores. • Such Entropic Frustration can be relieved by addition of solute (e.g. CO 2 ), enhancing the overall solvation .

Synthesis of NIMs OH OH OH OH OH OH OH OH Average 5-12 chains/nm 2 → + Silica Polymer NIMS H 3 C NH 2 O H 3 C : O O y x CH 3 Molecular Weight ( M w ): 600 ~ 2000

Estimation of Corona Density Corona fraction = 7 nm(dia.) Silica average surface area: 345 m 2 /g 12 nm(dia.) Silica average surface area: 220 m 2 /g 22 nm(dia.) Silica average surface area: 140 m 2 /g (Ref.:Sigma-aldrich) Average 12 chains/nm 2 Average 7.8 chains/nm 2 Average 5 chains/nm 2 Average diameter 7 nm Average diameter 22 nm Average diameter 12 nm Corona Density = f [Hydroxyl ions of Silica]

HSQC Spectra (Polyetheramine) H6 *Up (Red): CH or CH 3 9 *Down (Blue): CH 2 3 4 1 2 5 7 8 H1 H9 6 Jeffamine M-600 (M w . 600) H8 H7 Jeffamine M-600 in DMSO- d 6 C6 C9 H9 ‒ C9 H8 ‒ C8 C8 C1 H7 ‒ C7 H7 ‒ C7 C7

̶ ̶ ̶ ̶ ̶ ̶ ̶ ̶ HSQC Spectra (NIMS) *Up (Red): CH or CH 3 SO 3 9 SO 3 O 3 S *Down (Blue): CH 2 3 4 5 H6, H9 1 2 7 8 O 3 S SO 3 ** Electronegativity O: 3.44 6 Ionic Bond O 3 S SO 3 H1 SO 3 NIMS (M w . 600, 7 nm) N: 3.04 H6 ‒ C6/H9 ‒ C9 NIMS (7 nm SiO 2 with Jeffamine M-600) in DMSO- d 6 The peaks were deshielded ( 1 H shifted to higher ppm region) C6, C9 due to the approach of oxygen atoms in sulfonate group by the formation of Ionic Bonds H8 ‒ C8 C1 H7 ‒ C7

CO 2 capture by NIMS: Characterization of Different Core Size NIMs 7 nm core 12 nm core 22 nm core TEM : Mono-dispersed, Non-agglomerated nanoparticles TGA : Improved Thermal Stability ATR-IR : Counter Ions Grafted on Surface of Nanoparticles

Scheme of experimental setup Holder for thin layer samples sample Water bath P (at equilibrium and low pressure) 19 T

Effects of T and P on CO 2 Capture by NIMs (35 ℃, P CO2 =0.31MPa ) (35 ℃, P CO2 = 0.07-0.34 MPa ) • >95% of capacity in 20 min • Equilibrium in 50 min (35 ℃ , P CO2 =0.31 MPa) • Negligible effect of core Size • Pressure ↑ CO 2 absorption ↑ • Temperature ↑ CO 2 absorption ↓ (25 ℃ -65 ℃, P CO2 =0.31 MPa)

Regeneration of NIMs Vacuum (25 ℃, P CO2 =0.31MPa ) • Regenerated under vacuum for 20 min • A multi-cycle test: Regenerated NIMS shows SAME CO 2 capacity as a fresh sample

CO 2 Capture Mechanism of NIMs 1. Molecular Interaction btw. functional groups and CO 2 e.g., Lewis interaction btw. anion and CO 2 , other chemisorption (i.e. ‒ NH 2 )  Attenuated Total Refraction (ATR) FTIR and NMR Experiment 2. Molecular Structure e.g., Free volume for physisorption of CO 2  Atomic Force Microscopy (AFM) and 2D NMR Experiment  Volume vs Temperature measurement, ATR IR

NMR and ATR FTIR Spectra of NIMS with CO 2 13 C NMR result of NIMS with CO 2 Attenuated Total Reflection (ATR) IR results of NIMS with CO 2 (@ 25 ℃ and 10 bar) (@ 25 ℃ and 5 bar) Physically absorbed CO 2 CO 2 Chemically absorbed CO 2 200 180 160 140 120 100 80 60 40 20 0 ppm 3000 2500 2000 1500 1000 500 -1 ) Wavenumber (cm

ATR FTIR Measurement 1.0 0.8 Absorbance 0.6 0.12 0.4 0.10 0.25 0.2 Absorbance 0.08 0.20 0.0 1300 1200 1100 1000 900 Absorbance -1 ) Wavenumber (cm 0.15 0.06 0.10 0.04 0.05 680 670 660 650 640 630 -1 ) Wavenumber (cm 0.00 2400 2380 2360 2340 2320 2300 2280 -1 ) Wavenumber (cm 3000 2500 2000 1500 1000 500 -1 ) Wavenumber (cm

Lewis Acid-Base Interaction < ν 2 Bending Mode Region> NIMS + CO 2 : Eliminating Degeneracy of CO 2 Bending Mode Vapor CO 2 <Curve Fit Spectrum of ν 2 Bending Mode Region> NIMS + CO 2 SiO 2

Comparison of CO 2 Capture by NIMS & other media 100 #1 (16 hr,0.05g) #2 (16 hr,0.05g) [BMIM]BF4 (0.05g) #3 (16 hr,0.05g) #4 (16 hr,0.05g) [BMIM]PF6 (0.05g) #5 (16 hr,0.05g) #6 (16 hr,0.05g) 90 #7 (16 hr,0.05g) TSIL (0.05g) #8 (16 hr,0.05g) P/Po, % #2 (8 hr,0.1g) [BMIM]PF6 (12 hr,0.1g) [BMIM]BF4 (8 hr,0.1g) NIMS #2 (0.05g) 80 TSIL (16 hr,0.05g) 30% MEA (16 hr,0.05g) • NIMS#2 made with NIMS #2 (0.1g) NIMS#2 is a NIMS made with diamine polymer Diamine polymer 70 30 % MEA (0.05g) • 0.05 g of NIMS at 300K and 2 atm 0 200 400 600 800 1000 • TSIL: [HNH 2 MPL] NTF Time (Minute) Viscosicty = f [size of core, MW of polymer, ratio of core to polymer]

CO 2 Capture by NIMS#2: Effect of Temperature Temperature Absorption • Higher temperature 100 reduces viscosity 87 o C while physisorption 95 decreases. 300K 305K 310K P/Po % 315K 57 o C 320K • Up to 57 o C , initial 90 330K 340K reaction rates remain 350K 360K similar. 85 • Potential to operate 27 o C 80 at high temperature. 0 200 400 600 800 1000 1200 1400 1600 Time (Minute) (NIMS #2, 0.05 g of NIMS, 2 atm)

Future directions • Development of Multifunctional smart particles (e.g. capture carbon and sulfur at the same time) • Integrated systems (e.g. chemical looping technologies, ZECA, and enhanced WGS using mineral carbonation) • Process intensification and flexibility (production of heat, electricity, chemicals and fuels (e.g. hydrogen and liquid fuels) in any combination

Acknowledgement The NIMs part of this project is supported by Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST) as a part of the Global Research Partnership Center led by Cornell University.

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