1. Technology for a better society CO 2 separation and utilization via dual-phase high-temperature membranes Wen Xing 1, Thijs Peters 1, Marie-Laure Fontaine 1, Rahul Anantharaman 2, Anna Evans 3, Truls Norby 3, Rune Bredesen 1 1 SINTEF Materials and Chemistry 2 SINTEF Energy 3 Department of Chemistry, University of Oslo

2. Technology for a better society 2 Dual phase + CO 2 + membrane Increasingly interesting !! Scopus New type of membranes SINTEF, ASU, Newcastle University…

3. Technology for a better society 3 CO 2 permeable inorganic porous membranes Reproduced from talk by Y.S.Lin, July 10, 2013 Pittsburgh, Pennsylvania High temperature Non porous membrane 100% selective Or partially selective to both CO 2 and O 2 Dual-phase CO2 separation membrane

4. Technology for a better society 4 Potential applications of membranes Pre- and post- combustion CO 2 capture Efficient thermal integration Expected higher stability towards contaminants Catalytic membrane reactor e.g. dry reforming of methane CO 2 + CH 4 → 2H 2 + 2CO CO 2 +H 2 + H 2 O CO 2 CO 2 +N 2 +O 2 +H 2 O CO 2 Flue gas: CO 2 +N 2 +O 2 CH 4 2 H 2 + 2 CO Pre- combustion Post- combustion syngas CO 2 + 2CH 4 + O 2 → 3H 2 + 3CO+H 2 O Dry reforming Dry reforming combined with POX Anderson, M. and Y. S. Lin (2013). AIChE Journal 59(6): 2207-2218.

5. Technology for a better society Non-electronically conducting oxides support infiltrated with Na+ ion conducting melts One example of dual-phase membrane for pre- combustion decarbonization Molten salts (eutectic mixtures of carbonates …) CeO 2

6. Technology for a better society 6 Membranes controlled by transport contribution from melt and solid phase Pure ionic Pure electronic CO 3 2- e-e- CO 2 :O 2 = 2:1 CO 3 2- O 2- CO 2 CeO 2 YSZ Metal CO 2 e-e- Mixed conductors Mixed ionic & el. CO 3 2- O 2- CO 2 + O 2 mixture CO 2 + O 2 Gradient Molten salt

7. Technology for a better society 7 Performance Depending on vol.% of carbonates infiltration -Increasing in carbonate vol.% resulting in increased CO2 flux and decrease the mechanical strength Membrane thickness: 1 mm Feed side: 20% CO 2 + 20% He + 60% N 2 Sweep side: 99.999% Ar Temperature: between 650 and 550 °C Depending on electronic conduction of the matrix -transport both CO 2 and O 2

8. Technology for a better society 8 Effect of steam Membrane thickness: 1 mm Feed side: 20% CO 2 + 20% He + 60% N 2 Sweep side: Ar + 2.5% steam Temperature: between 650 and 550 °C Depending on the steam content in feed and sweep sides -Increasing steam content in feed and sweep side increases CO 2 flux -The increase is more significant by introducing steam to the sweep side

9. Technology for a better society 9 Oxide ion addition in molten phase Membrane thickness: 1 mm Feed side: 20% CO 2 + 20% He + 60% N 2 Sweep side: Ar + 2.5% steam Temperature: 550 °C CsVO 3 : MoO 3 = 3:1 (molar) CsVO 3 +MoO 3 : (Li 0.62 K 0.38 ) 2 CO 3 = 1:5 (weight) Depending on the oxide ion addition Oxide ion addition enhance the CO 2 flux under "dry" conditions (0.01% steam). Under higher steam condition, the steam effect dominates

10. Technology for a better society 10 1 month Long term stability in reducing atmosphere In CO 2 + He + N 2 at feed side Ar in sweep side 550 °C Feed : 20% CO 2 + 20%H 2 +20% He + 40% N 2 Sweep : 99.999% Ar 550 °C Introducing H 2 to the feed side Stable region

11. Technology for a better society 11 Process integration and modeling for a 400MW plant No captureMEA capture Dual-phase membrane Net power output (MW)416.4354.3~333 Net ele. Eff. % LHV58.1349.46~46.5 Eff. Penalty %08.67~11.5 Modelling of post-combustion with NGCC Membrane thickness: 0.1mm Membrane temperature: 500 to 550 °C Operation methods: -Post combustion (NGCC): with steam sweep -Pre combustion (IGCC): without sweep (~35 bar in feed) Details can be found in poster: Rahul Anantharaman et.al.

12. Technology for a better society 12 Process integration and modeling for a 400MW plant Details can be found in poster: Rahul Anantharaman et.al.

13. Technology for a better society The estimated membrane area: 13202 m 2 (decreases with increasing flux) for a 400MW plant. 13 Cost estimation Molten phase cost (less dominating): -carbonates/salt (low cost) -Infiltration process is simple and low cost (dip-coating) Porous support cost: ? Depends on materials and microstructure /processing

14. Technology for a better society Dual-phase CO 2 separation membranes provide high CO 2 selectivity (500 to 900 °C). Potential for CO 2 capture and membrane reactor for chemical production. Stable operation for ~1500 h demonstrated. Assessment of integration of membranes in a 400MW power plant : - for post-combustion (NGCC): less efficient as compared to MEA capture - for pre-combustion (IGCC): outperformed selexol capture 14 Summary

15. Technology for a better society Acknowledgements 15 The support from the Research Council of Norway (RCN) through the CLIMIT program (project number 207841) is gratefully acknowledged. DECARBIT project The support from the European Commission through the FP7/2007-2013 under grant agreement n° 211971

16. Technology for a better society Additional info. 16

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19. Technology for a better society 19 Fabrication of planar membranes 1 mm thick sample Dip-coating in molten carbonates at 600°C (Li 0.62 K 0.38 ) 2 CO 3 CeO 2 Carbonates Polymer nanoparticles Corn starch Chitosan Best result ! 100 µm 10 µ 10µm

20. Technology for a better society 20 Pressure tolerance calculation J. Electrochem. Soc., Vol. 144, No. 3, March 1997

21. Technology for a better society 21 What can be achieved by understanding this?

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