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

Transcription

1 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

2 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

3 Coal-fired Power Plants

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

5 Gasification-Based Energy Production System Concepts Fly Ash By-Product Sulfur By-Product Slag By-Product Steigel and Ramezan, 2006

6 Petroleum-based vs. Synthetic Liquid Fuels Crude Oil Price ($/Barrel) Steynberg, (2006) Crude oil prices once again at 1973 levels $81.81 (04/28/10) US$ of the day (Nominal) 2003 US$ (Real)

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

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

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

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

11 What is NIMS? Nanoparticle Ionic Materials A Nanoscale Analogue to Ionic Liquids + = Nanoparticle Ionic Corona Zero Vapor Pressure NIMS advantages >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.

12 Synthesis of NIMs OH OH OH OH OH OH OH OH Average 5-12 chains/nm 2 Polymer + Silica NIMS : C H 3 O y x O C H 3 O CH 3 NH2 Molecular Weight (M w ): 600 ~ 2000

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

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

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

16 ATR-IR: Counter Ions Grafted on Surface of Nanoparticles 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

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

18 Effects of T and P on CO 2 Capture by NIMs (35, P CO2 =0.31MPa) (35, P CO2 = 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)

19 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

20 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

21 NMR and ATR FTIR Spectra of NIMS with CO 2 13 C NMR result of NIMS with CO 2 (@ 25 and 5 bar) Attenuated Total Reflection (ATR) IR results of NIMS with CO 2 (@ 25 and 10 bar) Physically absorbed CO 2 CO 2 Chemically absorbed CO ppm Wavenumber (cm -1 )

22 ATR FTIR Measurement Absorbance Absorbance Wavenumber (cm -1 ) Absorbance Wavenumber (cm -1 ) Wavenumber (cm -1 ) Wavenumber (cm -1 )

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

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

25 CO 2 Capture by NIMS#2: Effect of Temperature P/Po % Temperature Absorption 87 o C 57 o C Higher temperature reduces viscosity while physisorption decreases. 300K 305K 310K 315K 320K 330K 340K 350K 360K Up to 57 o C, initial reaction rates remain similar Time (Minute) (NIMS #2, 0.05 g of NIMS, 2 atm) 27 o C Potential to operate at high temperature.

26 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

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

28 Thank you