Salt/Zeolite Composite Materials for Thermochemical Energy Storage Steffen Beckert Roger Gläser

Transcription

1 Salt/Zeolite Composite Materials for Thermochemical Energy Storage Steffen Beckert Roger Gläser Institute of Chemical Technology Universität Leipzig Symposium Dynamische Sorptionsverfahren Leipzig, May 30, 2017

2 Heat consumption and solar irradiation over the year (Patrick Pleul) 2

3 Outline Thermochemical Heat Storage Experimental Setup Salt/Zeolite Composites Numerical Modelling Conclusion and Outlook 3

4 Thermochemical Heat Storage A B + Q (s) Charge Discharge A + (s) B (g) Storage Chemical Reaction Metallic Hydrides Carbonate Systems Hydroxide Systems Redox Systems Ammonia Systems Organic Systems Absorption Hygroscopic salts o CaCl 2, MgCl 2, LiCl o MgSO 4 o NaOH o LiBr o Adsorption Silica Gels Metalaluminophosphates MOFs Zeolites Current systems still cover a wide range of required conditions for a large area of application. P. Pardo, A. Deydier, Z. Anxionnaz-Minvielle, S. Rougé, M. Cabassud, P. Cognet, Renew. Sust. Energ. Rev. 32 (2014) ; P. Tatsidjodoung, N. Le Pierrès, L. Luo, Renew. Sust. Energ. Rev. 18 (2013)

5 Thermochemical Heat Storage Chemical Reaction Metallic Hydrides Carbonate Systems Hydroxide Systems Redox Systems Ammonia Systems Organic Systems Absorption Hygroscopic salts o CaCl 2, MgCl 2, LiCl o MgSO 4 o NaOH o LiBr o Adsorption Silica Gels Metalaluminophosphates MOFs Zeolites Recent Developments Tailoring and Fine Tuning for Designated Applications Combination of Different Material Concepts Increasing the Heat Storage Density for Solar Applications P. Pardo, A. Deydier, Z. Anxionnaz-Minvielle, S. Rougé, M. Cabassud, P. Cognet, Renew. Sust. Energ. Rev. 32 (2014) ; P. Tatsidjodoung, N. Le Pierrès, L. Luo, Renew. Sust. Energ. Rev. 18 (2013)

6 Tailoring and Fine Tuning for Designated Applications (I) Shaping Pelletizing/Granulating Coatings K. Schumann et al., Chem. Ing. Tech. 86 (2014) ; Microporous Mesoporous Mater. 154 (2012) ; G.M. Munz et al., Appl. Therm. Eng. 61 (2013) ; S.K. Henninger et al., Renew. Energ. (2016) DOI: /j.renene

7 Tailoring and Fine Tuning for Designated Applications (II) Reducing the regeneration temperature (solar applications < 120 ºC) Decreasing the hydrophilic potential of the material Aluminophosphates (AlPOs): AlPO 4 Silico-Aluminophosphates (SAPOs): (Si x Al y P z )O 2 Zeolites: Variation of the Si/Al ratio during synthesis; Dealumination J. Jänchen, H. Stach, U. Hellwig, in: Studies in Surface Science and Catalysis, 2008, pp ; T.H. Herzog, J. Jänchen, E.M. Kontogeorgopoulos, W. Lutz, Energy Procedia 48 (2014)

8 Tailoring and Fine Tuning for Designated Applications (III) Salt/Zeolite Composites Adsorption Zeolite + Water Composite Salt/Zeolite + Water Absorption Salt + Water kw h m kw h m -3 (thermodynamically) Change in Heat Storage Density / % MgSO 4 /Na-X (Whiting 2013) MgSO 4 /Na-Y (Whiting 2013) MgCl 2 /Na-MOR (Whiting 2014) Salt Content / wt.-% G.T. Whiting, D. Grondin, S. Bennici, A. Auroux, Sol. Energy Mater. Sol. Cells 112 (2013) G.T. Whiting, D. Grondin, D. Stosic, S. Bennici, A. Auroux, Sol. Energy Mater. Sol. Cells 128 (2014)

9 Outline Thermochemical Heat Storage Experimental Setup Salt/Zeolite Composites Numerical Modelling Conclusion and Outlook 9

10 Thermochemical Characterization I Dry Air Sorption Chamber Humidity Management 10

11 Thermochemical Characterization II Sorption Enthalpy Thermocouples: Heat Storage Density Thermal Output Power Humidity Sensors: Water Loading Lift 11

12 Operating Conditions and Measurement Uncertainty Temperature (both sorption and desorption): ºC Humidity (30 ºC): < g kg -1, < mbar (40 ºC: 50 g kg -1, 74 mbar) Sample volume: 2 17 cm 3 (e. g., ca g zeolite) Material size : ~ mm (from grains over granulates to foams) Pressure: ambient pressure Parameter Measurement Uncertainty / % Water Loading Lift 6 Heat Storage Density 7 Water Sorption Enthalpy 5 Thermal Output Power

13 Typical Cycling Profile Temperature / C Humidity / (g kg -1 ) T1 (Reactor Inlet) T2 (Bulk 1) T3 (Bulk 2) T4 (Bulk 3) T5 (Reactor Exit) T6 (Surounding) X2 (Reactor Inlet) X4 (Reaktor Exit) Time / h 13

14 Outline Thermochemical Heat Storage Experimental Setup Salt/Zeolite Composites Numerical Modelling Conclusion and Outlook 14

15 Thermochemical Heat Storage with Salt/Zeolite Composites Thermochemical Properties Higher or Lower Heat Storage Density Various Methods/Conditions Composite Composition FAU, LTA, MOR + MgSO 4, MgCl 2, CaCl 2 Literature Present Work Salt/Zeolite Composites FAU + MgSO 4, CaCl 2, LiCl Variation of Salt Loading Composite Salt/Zeolite + Water Characterization Blocking of Zeolitic Micropores by Salt Relation of Thermochemical and Material Properties Characterization Structural, Textural Properties (XRD, SEM, N 2 Sorption, Hg Intrusion) Thermochemical Properties Conditions Close to Application Variation of Sorption Humidity S. Hongois, F. Kuznik, P. Stevens, J.J. Roux, Sol. Energy Mater. Sol. Cells 95 (2011) G.T. Whiting, D. Grondin, D. Stosic, S. Bennici, A. Auroux, Sol. Energy Mater. Sol. Cells 128 (2014) G. Whiting, D. Grondin, S. Bennici, A. Auroux, Sol. Energy Mater. Sol. Cells 112 (2013)

16 Binderless Zeolite Granulates Zeolite Powder Zeolite Granulate K. Schumann, B. Unger, A. Brandt, F. Scheffler, Micropor. Mesopor. Mats. 154 (2012)

17 CaCl 2 and MgSO 4 Composites: SEM Ca-X 23CaCl 2 /Ca-X Pore Volume / (cm 3 cm -3 ) Micropores (~ 1 nm) Secondary Pores (4 nm...10 µm) CaCl 2 /Ca-X Mg-X 14MgSO 4 /Mg-X 24MgSO 4 /Mg-X Salt Content / (mol mol -1 ) Salt is Predominantly Located Inside the Micropores (Salt Inclusion) R.M. Barrer, W.M. Meier, J. Chem. Soc. (1958) R.M. Barrer, A.J. Walker, Trans. Faraday Soc. 60 (1964)

18 CaCl 2 Composites: XRD Intensity / arb. u. Rel. Intensity Faujasite / 23CaCl 2 /Ca-X 15CaCl 2 /Ca-X 8CaCl 2 /Ca-X Ca-X Na-X CaCl 2 / CaCl 2 2 H 2 O CaCl 2 4 H 2 O ( ) / ( ) CaCl 2 6 H 2 O 18

19 Thermochemical Properties (MgSO 4 /Mg-X Composites) Water Loading Lift / (g cm -3 ) Available Pore Volume Salt Content / wt.-% Heat Storage Density / (kwh m -3 ) Salt Content / wt.-% Humidity: 3, 6, 9, 12, 15, 21 g kg -1 Included Salt Ions Can Not Be Hydrated Reduced Water Uptake 19

20 Thermochemical Properties (CaCl 2 /Ca-X Composites) Water Loading Lift / (g cm -3 ) Salt Content / (mol mol -1 ) Time Humidity: 3, 6, 9, 12, 15, 21 g kg -1 Formation of a Salt Solution Above the Deliquescence Humidity (CaCl 2 : ~8 g g -1 ) within the Secondary Pore System Three Phase Equilibrium (Included Salt, Salt Solution, Water Vapor) Pore Volume Limits the Water Uptake 20

21 Further Improvements: Ongoing Work Lower Deliquescence Humidity 300 Heat Storage Density / (kw h m -3 ) Larger Secondary Pore Volume Salt Content / (mol mol -1 ) Reducing the Inclusion 21

22 Outline Thermochemical Heat Storage Experimental Setup Salt/Zeolite Composites Numerical Modelling Conclusion and Outlook 22

23 Experimentalist s View Microscopic Material Properties Structure Intensity / arb. u / Texture Pore Volume / (10-2 cm 3 cm -3 ) Micropores (~ 1 nm) Secondary Pores (4 nm...10 µm) Salt Content / wt.-% Thermochemical Material Properties Lab Water Uptake / (g cm -3 ) Heat Storage Density / (kw h m -3 ) Macroscopic Material Properties Salt Content / (mol mol -1 ) Salt Content / (mol mol -1 ) Application 23

24 General Aspects of Numerical Modelling Experimental Input OpenGeoSys: Open Source Simulation Software for Multi-Physical Modelling T. Nagel, S. Beckert, C. Lehmann, R. Gläser, O. Kolditz, Appl. Energy 178 (2016) ; H. Shao, T. Nagel, C. Roßkopf, M. Linder, A. Wörner, O. Kolditz, Energy 60 (2013) ; T. Nagel, H. Shao, A.K. Singh, N. Watanabe, C. Roßkopf, M. Linder, A. Wörner, O. Kolditz, Energy 60 (2013)

25 Dubinin-Polanyi Theory Adsorption Potential: Adsorbed Volume: Output A m = R T ln p s M Ads p (A m ) = C eq(t) ߩ Ads T Experimental Input Density Model Water Uptake / g g Water Sorption Isotherm 25 C 50 C 70 C 100 C 130 C 150 C 180 C 200 C 250 C Characteristic Curve Pressure / mbar 25

26 Adsorbate Density Models (I) T. Nagel, S. Beckert, N. Böttcher, R. Gläser, O. Kolditz, Energy Procedia 75 (2015) , C. Lehmann, S. Beckert, R. Gläser, O. Kolditz, T. Nagel, Appl. Energy (2015) DOI: /j.apenergy

27 T s / Jg 1 h / Jg 1 T s / Jg 1 h / Jg 1 Adsorbate Density Models (II) Desorption: T = 180 ºC p W = 0 mbar Adsorption: T = 20 ºC p W = 10 mbar T. Nagel, S. Beckert, N. Böttcher, R. Gläser, O. Kolditz, Energ. Procedia 75 (2015) ; C. Lehmann, S. Beckert, R. Gläser, O. Kolditz, T. Nagel, Appl. Energy (2015) DOI: /j.apenergy

28 Heat Storage Density Numerical Modelling vs. Experiment Desorption: T = 110 ºC Adsorption: T = 30 ºC p W = 0.2 mbar p W = mbar Heat Storage Density / (kwh m -1 ) Ca-X, exp Na-X, exp Ca-X, calc Na-X, calc Water Vapour Partial Pressure / mbar C. Lehmann, S. Beckert, T. Nonnen, J. Möllmer, R. Gläser, O. Kolditz, T. Nagel, accepted for publication in Energy Procedia (2017) 28

29 Outline Thermochemical Heat Storage Experimental Setup Salt/Zeolite Composites Numerical Modelling Conclusion and Outlook 29

30 Salt/Zeolite Composites: Conclusions and Outlook Ion Exchange Necessary Prior Impregnation Salt Inclusion Below Deliquescence Humidity Lower Heat Storage Density Formation of a Salt Solution Above Deliquescence Humidity Higher Heat Storage Density Conclusions Outlook Tuning the Composites for the Use at Low Humidities by, e.g., Salt Mixtures Composite Salt/Zeolite + Water Regulation Strategies Need to be Adapted to Material Properties Reduce Salt Inclusion Lower Donnan-Potential e.g., Less Hydrophilic Zeolites Larger Secondary Pore Volume for Increased Water Uptake Capability and Increased Heat Storage Density by Modifying of the Granulation Process 30

31 Thank You for Your Attention EnErChem (FKZ: 03ESP402)