Carbon Dioxide Separation Using Ionic Liquids. Dr. Dilip Raut Prof. Jyri-Pekka Mikkola research group
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1 Carbon Dioxide Separation Using Ionic Liquids Dr. Dilip Raut Prof. Jyri-Pekka Mikkola research group 1
2 Biogas is a valuable alternative energy resource Sources: sewage digesters, biowaste digesters, landfills Application area: heat and electricity Waste-to-energy concept Sweden and Germany occupy the leading positions in biogas production sector 2
3 Biogas composition CH 4 (40-60 vol. %), CO 2 (25 45 vol. %), 2 (1-15 vol. %), others (< 1 vol. %) Others: numerous S-containing compounds, siloxanes, aromatic, halogenated compounds... Biogas upgrading: Increasing the heating value Improving of biogas quality 3
4 Current research in the field Biogas Production Biogas Upgrading umber of publications Publication year biogas production biogas upgrading 4
5 The main methods for removal of carbon dioxide Chemical solvent scrubbing Physical solvent scrubbing Chemical mineral trapping Adsorption Cryogenics
6 ew process for removing CO 2 using an ionic liquid absorbent What is an ionic liquid? Briefly... Structure CH 3 H 3 C P e.g. [bmim][b 4 ] The most important properties: They are salts that are fluid over a wide temperature range including room temperature egligible vapor pressure (nonvolatile), often with thermal stability to over 350 ºC Properties are adjustable, adding flexibility to this class of solvents Perspective on Green Chemistry 6
7 Switchable ionic liquids heat, 2 8-diazabicyclo[5.4.0]undec-7-ene (DBU) Poly(ionic liquid)s poly[2-(1-butylimidazolium-3-yl)ethyl methacrylate hexaflurophosphate E. Privalova, M. urmi, M. S. Marañon, E. V. Murzina, P. Mäki-Arvela, K. Eränen, D. Yu. Murzin, J.-P. Mikkola. CO 2 removal with switchable versus classical ionic liquids. Sep. Purif. Technol. 97, (2012), E. Privalova, E. Karjalainen, M. urmi, P. Mäki-Arvela, K. Eränen, H. Tenhu, D. Yu. Murzin, J.-P. Mikkola. Imidasolium-based poly(ionic liquid)s as 7 a new alternative for CO 2 capture. ChemSusChem. (Accepted)
8 Switchable ionic liquid* Switchable ionic liquids (SILs) heat, 2 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) An ionic liquid formed upon CO 2 bubbling o cumbersome synthesis required + CO 2 - CO 2 Low-Polarity Solvent High-Polarity Solvent * D. Heldebrant et al. Energy Environ. Sci., 2008
9 CO 2 capture with novel solvents (ILs vs. SILs) Conditions: P = 1 bar, T = 298 K, V L = 2 ml CO 2 loading, mol CO 2 / mol IL B O O B [C 4 mim][b 4 ] Time, min [C 4 mim][acetate] CO 2 loading, mol CO 2 / mol ROH DBU + 1-hexanol Time, min DBU + 6-amino-1-hexanol DBU + 4-amino-1-butanol DBU + L-valinol DBU + L-prolinol CO 2 loading of SILs CO 2 loading of ILs 2 E. Privalova, M. urmi, M. S. Marañon, E. V. Murzina, P. Mäki-Arvela, K. Eränen, D. Yu. Murzin, J.-P. Mikkola. CO 2 removal with switchable versus classical ionic liquids. Sep. 9 Purif. Technol. 97, (2012)
10 Viscosity measurements HO H 2 HO Viscosity, [Pa*s] HO amino-1-butanol amino-1-hexanol H 2 B [C 4 mim][b 4 ] B H [C 2 4 mim][acetate] O O H L - prolinol 1-hexanol H 3C CH 3 H 2 L - valinol OH OH OH H 3C 1-hexanol H CH 3 OH H 2 L - valinol L - prolinol 4-amino-1-butanol OH HO OH H 2 6-amino-1-hexanol without CO 2 bubbling after CO 2 bubbling After CO 2 capture, the viscosity slightly decreased in the case of the studied ionic liquids In case of SILs (DBU + ROH) mixtures, the viscosity dramatically increased It was observed that a rise in temperature provides an attractive decline in the viscosity of SILs An increase in temperature from 298 to 328 K decreased the viscosity of the mixture (CO 2 + DBU + 4- amino-1-butanol) by a factor of 20 while for a less viscous mixture (CO 2 + DBU + 1-hexanol) the viscosity changed by a factor of 10. E. Privalova, M. urmi, M. S. Marañon, E. V. Murzina, P. Mäki-Arvela, K. Eränen, D. Yu. Murzin, J.-P. Mikkola. CO 2 removal with switchable versus classical ionic liquids. Sep. Purif. Technol. 97, (2012)
11 Conclusions Ionic liquids appeared to be promising sorbents in case of both CO 2 and volatile organic compounds removal. Switchable ionic liquids are sorbents that combine high CO2 capturing efficiency with the advantages of simple synthesis. In terms of CO2 removal efficiency, the switchable ionic liquids were found clearly superior to classical ionic liquids (by a factor of two). The study also revealed some of the structural effects of various mixtures based on DBU and (amino) alcohols.
12 Collaboration: The financial support by the Academy of inland and the innish unding Agency for Technology and Innovation (TEKES), The Bio4Energy programme, The COST action CM0903 UbioChem are gratefully acknowledged
13 Thank you 13
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