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Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed C. Rokopf, M. Haas, M. Linder, A. Wrner German Aerospace Center (DLR), Stuttgart, Germany www.DLR.de Slide 2 > 7 th World


  1. Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed C. Roßkopf, M. Haas, M. Linder, A. Wörner German Aerospace Center (DLR), Stuttgart, Germany

  2. www.DLR.de • Slide 2 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Thermochemical Heat Storage Application & Potential Application: - Storage of industrial waste heat - Reduction of energy generation cost - Base load capability of renewable energy systems Potential: - High storage densities - Long-term and loss-free storage - Heat release at any time - Possibility of heat transformation

  3. www.DLR.de • Slide 3 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Thermochemical Heat Storage Reaction System Reversible Gas-Solid-Reaction: CaO (s) + H 2 O (g) ⇌ Ca(OH) 2(s) + 99,5 kJ/mol Temperature range ~ 400-700 ° C  Main advantage: Low price (55-65 € / ton) - Poor thermal conductivity and permeability of CaO/Ca(OH) 2  High demand on reactor geometry leads to high costs  Adjustment of reactor to required power  Supply of capacity in cheap tanks  Material flow through the reactor is essential!

  4. www.DLR.de • Slide 4 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Motivation Separation of Power and Capacity CaO (s) / Ca(OH) 2(s) Heat transfer Process integration Process integration fluid Heat transfer CaO (s) / fluid Ca(OH) 2(s) Heat transfer fluid Heat transfer fluid CaO (s) / Ca(OH) 2(s) H 2 O (g)

  5. www.DLR.de • Slide 5 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Challenge Poor Powder Properties Reaction Bed Heat Conduction Low thermal conductivity vs Poor flowability Heat Flux v Reaction Bed HTF HTF Plate heat exchanger

  6. www.DLR.de • Slide 6 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Approaches  Pellets unstabile during  Increasing the cycling roughness of particle surface

  7. www.DLR.de • Slide 7 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Modification of Material Increasing the Roughness of Surface Extension of Van-der-Waals Eq. : 𝑆 2 𝐷 𝐼 𝑆∙𝑠 R 𝐺 𝑊𝑊𝑊 = 𝑏 2 ( 𝑆+𝑠 ) + ( 2𝑏 𝑄 ) 2 ∙2𝑆 6 x 0 2h r  Increasing of the roughness of the surface x 0 α x 1 and distance between the particles by R addition of nano particles State of the art: - 1 Improving powder flowability in bulk and pharmaceutical industries - 2 Combination of nano particle agglomerates with CaO to improve fluidization behavior for CO 2 adsorption  Coating of Ca(OH) 2 by nano particles in order to improve flowability is uninvestigated 1 K.Köpker et al., Application of nano particles , Landesanstalt für Umwelt, Messungen und Naturschutz Baden-Wuerttemberg,2007 2 Pontiga et. al, Dry fas-solid carbonation in fludized beds of Ca(OH)2 and nanosilica/Ca(OH)2 at ambient temperature and low CO2 pressure, Chemical Engineering Journal, 2013

  8. www.DLR.de • Slide 8 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Dry particle coating Ca(OH) 2 + 0,5 - 15% Aerosil 300

  9. www.DLR.de • Slide 9 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Results of Material Modification Effects of Variable Power Inputs Aerosil 300 2% Compressive strength ( σ 1 =6000) / N/m² Aerosil 300 6% 3000 Aerosil 300 11% 2500 2000 1500 0 1000 2000 3000 4000 5000 6000 7000 Mixing intensity / U/min

  10. www.DLR.de • Slide 10 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Cycling stability Tests in pilot-scale reactor

  11. www.DLR.de • Slide 11 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Cycling stability After Cycling  Calcium silicates lead to - Reduction of storing capacity - Hardening of surface structure Roßkopf et al., Investigations of Nano Coated CaO/Ca(OH) 2 Cycled in Thermochemical Storage , in preparation

  12. www.DLR.de • Slide 12 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Conclusion & Outlook - Thermochemical Heat storage based on Ca(OH) 2 demands a flow-through of the reactor - Improvement of Ca(OH) 2 flowability by adding nano particles at ambient conditions is shown - Homogeneous flow through thermochemical reactor at room temperature achieved - Cycling stability is proven over 10 cycles in pilot-scale reactor  Flow behaviour during thermochemical reaction will be investigated

  13. www.DLR.de • Slide 13 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Thank you for your attention

  14. www.DLR.de • Slide 14 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Thermodynamic equilibrium

  15. www.DLR.de • Slide 15 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Storage densities Typical storage densities in kWh/m³: - Sensible, mortar, Δ T=50K 25 - 30 - Sensible, Water, Δ T=50K 50 - Latent, solid-liquid 50 - 100 - Physical oder chemical sorption 50 - 140 - Thermochemical reaction 100 – 700 - Storage capacity in 1 kg Ca(OH)2 0,373 Wh - Storage capacity of pilot-scale reactor ~200 kWh/m³

  16. www.DLR.de • Slide 16 > 7 th World Conference on Particle Technology > Christian Roßkopf • Improving Powder Flowability by Adding Nanoparticles for Thermochemical Heat Storage with Moving Reaction Bed > 19 th to 22 nd May 2014 Particle size Pelletizing the material - Increase of weight force by increasing the particles diameter  Problem: Volume change of the material by chemical reaction leads to tensions within the pellet  Cracking of the pellet after few cycles in thermochemical reactor

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