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

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

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

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 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):

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

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

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 % He + 60% N 2 Sweep side: % Ar Temperature: between 650 and 550 °C Depending on electronic conduction of the matrix -transport both CO 2 and O 2

Technology for a better society 8 Effect of steam Membrane thickness: 1 mm Feed side: 20% CO % 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

Technology for a better society 9 Oxide ion addition in molten phase Membrane thickness: 1 mm Feed side: 20% CO % 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

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 %H 2 +20% He + 40% N 2 Sweep : % Ar 550 °C Introducing H 2 to the feed side Stable region

Technology for a better society 11 Process integration and modeling for a 400MW plant No captureMEA capture Dual-phase membrane Net power output (MW) ~333 Net ele. Eff. % LHV ~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.

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

Technology for a better society The estimated membrane area: 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

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

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

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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

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

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

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