Membrane designs for Reverse Electrodialysis. David Vermaas Kitty Nijmeijer Membrane Science & Technology

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1 Membrane designs for Reverse Electrodialysis David Vermaas Kitty Nijmeijer Membrane Science & Technology

2 Membrane Science & Technology Group 2

3 Energy desalination 3 Thermodynamic minimum: 2.5 MJ/m 3 fresh water

4 Salinity Gradient Energy 4 transport Salinity Gradient Energy evaporation precipitation river discharge Sea River

5 Energy Potential 5 Waddenzee salt water IJsselmeer fresh water 200m Hydro electric power station

6 Energy Potential 6 Waddenzee salt water IJsselmeer fresh water 200m Hydro electric power station 50 elephants on 1 m 2

7 Energy Potential 7 Waddenzee salt water IJsselmeer fresh water 200m Hydro electric power station

8 Energy Potential 8 Theoretical potentials: Sacramento river: 1400 MW Mississippi river: 36 GW Worldwide: > 2 TW ( worldwide electricity consumption) Challenge: increase in power output Objective: - 5 kw/m 3 reactor volume - 5 W/m 2 membrane area

9 Principle of RED 9 Sea water e - Cl - Cl - Cl - e - Anode Na + Na + Na + Na + Cathode CEM AEM CEM AEM CEM AEM CEM River water

10 Opportunities for improvement 10 Membrane development Spacer / compartment solutions Lessons from and for other applications

11 Membrane properties and membrane design 11

12 Ion exchange membranes for RED 12 Cation exchange membrane (CEM) Source: ionics SO 3 Anion exchange membrane (AEM) N(CH 3 ) 3

13 Membrane properties 13 Dlugolecki et al., Journal of Membrane Science 319 (2008) 214.

14 Membrane design 14 G. M. Geise, M. A. Hickner and B. E. Logan, ACS Appl. Mater. Interf., 2013, 5,

15 Membrane design 15 CH 2 CHO y CH 2 CHO n-y CH 2 CH 2 Cl 2 CH 2 CHO + n CH 2 Cl y + + Cl - Cl - Charged polymer Polymer PECH Crosslinker DABCO CH 2 CH 2 CHO y CH 2 CHO n-y Source: Ionics CH 2 Cl P. Altmeier, Patent 5,746,917 (1998); Bolto and Jackson, Reactive polymers 2 (1984)

16 Membrane design 16 P dens OCV2 4 R Gross power density (W/m 2 ) Tailor-made membranes 75mV2 4 1Ωcm2 14W/m Flow rate (ml/min) E. Guler et al., ChemSusChem 5 (11) (2012) ; Journal of Membrane Science 446 (2013)

17 Membrane resistance 17 Membrane resistance increases at low concentrations Dlugolecki et al., Journal of Membrane Science 349 (2010) 369.

18 Membrane resistance 18 Geise, Curtis, Hatzell, Hickner and Logan, 2014, Env. Sci.&Techn. Letters, 1, 36-39

19 Membrane resistance 19 Galama, Vermaas, Veerman, Saakes, Rijnaarts, Post and Nijmeijer, 2014, J. Membr. Sci., 467,

20 Membrane resistance 20 Osmosis Galama, Vermaas, Veerman, Saakes, Rijnaarts, Post and Nijmeijer, 2014, J. Membr. Sci., 467,

21 Role of osmosis in electrodialysis 21 Galama et al., 2014, Desalination, 342, 61-69

22 Novel membrane designs 22 Controlled assembly of nanoparticles Negative surface charge creates cationselective membranes Electric double layers overlap in the nano-interstices Silica ( nm) and carboxylate polystyrene (100 nm) E. Choi, K. Kwon, D. Kim, J. Park MEMS 2014, San Francisco, CA, USA, January 26-30, 2014

23 Novel membrane designs 23 Nanoporous polycarbonate track-etch membrane Straight isoporous membrane (pore sizes: nm) Shown for CEM in two compartment cell: ~6 mw/cm 2 Monovalent cation Bivalent cation K. Kwon, S. J. Lee, L. Li, C. Han and D. Kim, Int. J. Energ. Res., 2013, 38, 530.

24 Bio-medical application 24 Charged silica nanochannels 7.7 W/m 2 Kim et al., 2010, Microfluid Nanofluid., DOI /s

25 Spacers and microstructured membranes 25

26 Spacer thickness 26 Effect spacer thickness - Fresh water major electrical resistance - Spacers blocks conductive area Vermaas et al., Environ. Sci. & Technol. (2011) 45 (16), pp

27 Spacer thickness 27 Decreasing spacer thickness D. Vermaas et al., Environ. Sci. & Technol. (2011) 45 (16), pp

28 Spacer thickness 28 Decreasing spacer thickness D. Vermaas et al., Environ. Sci. & Technol. (2011) 45 (16), pp

29 Creating microstructured membranes 29 E. Guler et al., Journal of Membrane Science 458 (2014) 136 D. Vermaas et al., Journal of Membrane Science (2011) D. Vermaas et al., Electrochimica Acta (2014)

30 Microstructured membranes hot pressing 30 Profiled CEM (Ralex - CMH) and AEM (Ralex - AMH) D. Vermaas et al., Journal of Membrane Science (2011)

31 Microstructured membranes for ED 31 Higher conductivity Strathmann, desalination, 2010, 264, Onset of overlimiting current Balster et al., J. Phys. Chem. B, 2007, 111,

32 Microstructured membranes 32 D. Vermaas et al., Journal of Membrane Science (2011)

33 Mixing promoters 33 D. Vermaas et al, 2014, J. Membr. Sci.,

34 Profile structures 34 a) b) c) d) Structured membrane Flat membrane 100 µm 100 μm 200 µm 200 µm E. Guler et al., Journal of Membrane Science 458 (2014) 136

35 Profile structures 35 a) ridge a) b) c) mm 0.4 mm 0.4 mm a) b) c) 0.2 mm mold 0.2 mm mold b) wave 0.8 mm 0.0 s 0.8 s 1.6 s 2.4 s mm 0.4 mm 0.4 mm ) c) 0.2 mm mold 0.2 mm mold 0.8 mm c) pillar 0.0 s 0.8 s 1.6 s 2.4 s mm 0.4 mm 0.8 mm 0.0 s 0.8 s 1.6 s 2.4 s 0.2 mm mold E. Guler et al., Journal of Membrane Science 458 (2014) 136

36 Profile structures 36 Flow rate (ml/min) Pillar 0.6 Net power density (W/m 2 ) Ridge Flat Wave Reynolds (-) E. Guler et al., Journal of Membrane Science 458 (2014) 136

37 Fouling: Easy to clean 37 Vermaas et al., Env. Sci & Techn. (2014) 3065-

38 Fouling: Easy to clean 38 Vermaas et al., Env. Sci & Techn. (2014) 3065-

39 Conclusion and perspective 39 Membrane chemistry allows tailoring the transport properties for specific applications Membrane resistance depends on concentration and osmosis Microstructured membranes facilitate ionic transport, increase net power density and are easy to clean

40 Acknowledgements Enver Guler, Piotr Długołęcki, Michel Saakes, Matthias Wessling, Yali Zhang, Rianne Elizen, Oane Galama, Joost Veerman, Jan Post 40 Wetsus Blue Energy Team Wetsus:

41 41 More information: Kitty Nijmeijer