This is ppt slides of my Ph.D research work, carried out in Kyung Hee University, Seoul 2007-2011.

1. Ionic Liquids for CO2, Light Olefins, and Alkynes Separation: Material Selection and Solubility Investigations Amabilis Jelliarko Palgunadi Advisers : Prof. HoonSikKim & Prof. Minserk Cheong Department of Chemistry Kyung HeeUniversity 1

2. 2 Thesis Outline Non-Task Specific Ionic Liquids (TSILs) and Task Specific ILs for CO2Capture: Material Design and Solubility Investigations. Room Temperature Ionic Liquids (RTILs) for Light Alkynes–Olefins (C2–C3) Separation: Material Selection and Solubility Investigation.

3. Introduction Reaction & Separation Media Analytical Chemistry Lubricants Ionic Liquids (ILs) Ionic in composition Inherent ionic strength Tailored structure Variable functional sites Negligible volatility Moderate polarity Electrical conductivity Liquid Crystals Heat Carriers Catalysts Electrolytes Advanced Materials Precursors 3

5. Cement industriesThe real challenge is to clean-up post combustion emissions from fossil fuels burning activities which contains 3–15% of CO2 at 1 bar. [1] http://cdiac.esd.ornl.gov/home.html

6. 5 Objective CO2 Capture Employing Room Temperature Ionic Liquids (RTILs) Established Liquid-based CO2 Scrubber System Power Plant–Coal Combustion   Room Temperature Ionic Liquids??

7. CO2 solubility Behavior in Non-Task Specific ILs [BF4]— [PF6]— In situ ATR-IR spectra of dissolved CO2in the bending mode region[1]–indication of Lewis acid-base interaction between CO2 and anion. [1] Chem. Commun. 20 (2000) 2047-2048; Combining Ionic Liquids and Supercritical Fluids: in situ ATR-IR Study of CO2 Dissolved in Two Ionic Liquids at High Pressures. 6 Solubility vsVolume Molar of RTIL According to simplified regular solution theory (RST), linear correlation between CO2 solubility vs molar volume of RTILs suggests that non-specific physical interaction plays dominantly

9. Customized structure

10. Simple reaction

12. Stable under constant 100 °C for 1 month.[Bu4N][BzAPr] [Bu4N][CyhexAPr] [Bu4N][BuAPr] [Bu4N][dEAEAPr]

13. Task Specific ILs Having Amino Acid Structure (AA–TSILs) 8 30 %wt in H2O 30 %wt in EG Recycle test (30 %wt in EG) FT-IR and NMR spectroscopies suggest the formation of ammonium carbamate and bicarbonate species (chemical interaction) in the solution when CO2 is absorbed.

14. CONCLUSIONS CO2solubilities in conventional RTILs are mostly controlled by weak, non-bonding interactions (i.e. van der Waals interaction). Non-TSILs cannot compete with alkanolamine for CO2 scrubbing due to their extremly weak interaction with CO2. To improve the CO2 absorption capacity, new IL-based chemical absorbents for CO2 having amino acid-like structure (AA–TSILs) have been synthesized. AA–TSILs may be promising alternative agents to conventional alkanolamine for CO2 capture. 9

15. Naphtha Cracking and Separation of Alkynes from Olefins Objective Naphtha Cracking  Separation Path  Acetylene Recovery Unit (Linde)  Room Temperature Ionic Liquids?? 10

16. Plausible Interaction Mode Between IL and Alkyne or Olefin 11 H-bond donor H-bond acceptor π···Hacidic bond H-bond donor Van der Waals interaction Alkyne and alkene Ionic Liquid pKa C2H2 << pKa C2H4 Kamlet—Taft polarity parameters: α = hydrogen-bond donor ability β = hydrogen-bond acceptor ability π* = polarity/polarizability

17. Solubility vsVolume Molar of RTIL Simplified RST model C2H4  YES C2H2  NO 12 Acetylene–Ethylene Solubility Behavior This linear correlation suggests that non-specific physical interaction plays dominantly in determining the gas solubility.

18. Acetylene–Ethylene Solubility Behavior Solubility vs H-bond Acceptor Ability (β) of RTIL Linear Solvation Energy Relationships for C2H2:Ln(KH) = -1.41b + 3.41 a and p* show negligible effects 13 Linear correlation βvsKH C2H4  NO C2H2  YES Solubility vs Enthalpy of Solvation for C2H2 Linear correlation ΔHvsKH C2H4  NO C2H2  YES

19. Solubility vsVolume Molar of RTIL Simplified RST model C3H6  YES C3H4  YES 14 Propyne–Propylene Solubility Behavior Solubility vs Enthalpy of Solvation Linear correlation ΔHvsKH C3H6  NO C3H4  NO

20. Material Selection for Optimal Separation [EMIm][Me2PO4] [EMIm][MeHPO3] [EMIm][Tf2N] Small RTIL’s Vm and high bvalue  High C2H2 selectivity 15 [DMIm][Tf2N] + C2H2 [DMIm][MeHPO3] + C2H4 [DMIm][MeHPO3] [DMIm][Me2PO4] [DMIm][MeSO4] [DMIm][MeHPO3] + C3H4 [DMIm][MeHPO3] + C3H6 Small RTIL’s Vm and more negative ΔH High C3H6selectivity [EMIm][Tf2N]

21. CONCLUSIONS C2H4 and C3H6solubilities are governed by solubility parameter of RTIL (in other words, weak, non-bonding interactions). C2H2solubility is determined by a specific acid-base interaction (H-bond interaction). C3H4 solubility is controlled by a trade-off between physical and chemical interactions. Higher separation selectivity for C2H2 and C3H4 may be achieved with smaller size of RTIL possessing higher HBA power (b) or ΔH of absorption, respectively. 16

22. 감사합니다 Acknowledgements Prof. HoonSik Kim, Prof. Minserk Cheong, Lab-Lovers, BK-21, National Energy Resources Technology Development R&D Program for Greenhouse Gas Mitigation-Korea Ministry of Knowledge Economy, Carbon Dioxide Reduction & Sequestration Research Center-21st Century Frontier Programs-Ministry of Science and Technology. 17