Trends in development of advanced porous materials for thermal adsorption storage of heat. Jochen Jänchen

Transcription

1 Trends in development of advanced porous materials for thermal adsorption storage of heat Jochen Jänchen

2 Outline Introduction Principle of thermochemical storage and heat transformation with solids Porous materials available, producer Modification strategies Examples of new thermal adsorption applications Results of actual research and development areas Conclusions

3 1. Introduction - A modern energy supply with rising share of renewables ask for new concepts, - Significant contributions are feasible to energy savings and a greener energy supply using thermal adsorption storage and heat transformation by tailored zeolites and other new hygroscopic materials, - Development of new manufacturing strategies to meet the specific requirements of the materials for those technologies, -New ideas for integrated storage systems

4 Principle, solid adsorbens Principle of thermal (ad)sorption storage and heat transformation Big advantage of the principle against sensible and PCM: It is appropriate for heating, cooling and drying!

5 World zeolite consumption in 2010 Annual synthetic zeolite consumption about 1 million tons (excluding China s >2.4 million tons natural zeolite consumption) NaA 750 Tt Waschmittel A, X 50 Tt Adsorption ZSM-5 10 Tt Beta ZSM-22 < 100 t T i-silicalit 100 t Mordenit 600 t USY 100 Tt NaP 50 Tt Waschmittel Problem: all this zeolite products are made for ion exchange, catalysis, as adsorbents for separation, for drying and purification processes. No big market for zeolites for thermal adsorption storage and heat transformation application yet.

6 Selection of manufacturer for molecular sieves Company Country Materials CWK, Bad Köstritz Germany Zeolite A, 13X, (binderless beads) Clariant/Bitterfeld Switzerland/ Germany LSX, SAPO-34, AlPO-5, Silicalite, TS-1, Beta, MOR (beads) Grace Davison USA/Germ. Silica gel, zeolite A bead Zeolyst USA Zeolite Y, Beta, MOR, ZSM-5, FER (powders) Zeochem AG Switzerland Zeolite A, 13X,Y, LSX, MOR, ZSM-5 (beads) Sterlitamak Catalyst Plant Shanghai Ston Ind. Co. Ltd. and very many others Russia China Zeolite A, 13X All standard zeolites, powders, bead

7 Materials available - zeolites Synthetic standard Zeolites: (Faujasites) LSX, 13X, NaY (Linde Type A) 4A, 5A Dealuminated NaY Zeotypes: AlPO-5 (AFI), SAPO-34 SAPO-11 Natural zeolites: Clinoptillolite, chabazite

8 Materials available other porous structures Composites (introduced by Y. Aristov, Novosibirsk): CaCl 2 nh 2 O in silica gel, charcoal, aluminosilicate, salts hydrates MgSO 4 nh 2 O Silica gel ( old-fashioned ) MCM-41 (mesoporous frameworks) MOF (metal-organic frameworks), ISE Freiburg O.M. Yaghi, California)

9 Modification strategies Zeolites: lattice modification (anion) and cation exchange Silica gel: pore and surface modification Composites: application of different salts Tuning of the hydrophilic character of highly porous structures - High discharging T and low evaporator T needes strong interaction: low Si/Al ratio, ion exchange with divalent ions (Ca, Mg, and others) -Low charging T needs less strong interaction: #AlPO s (and SAPO s);; medium hydrophilic lattice formend by Al and P, disadvantages in manufacturing (organic template) # or: changing of lattice composition by dealumination of the Y zeolite framework -Composites or hygroscopic salt hydrates (Y. Aristov, Russia or van Essen, Bach, Bakker, ECN; Rindt, TU Eindhoven, the Netherlands) such as - silica gel, aluminosilicates, activated carbon zeolites with CaCl 2 nh 2 O or MgSO 4 nh 2 O.

10 Example 1, cooling for comfort ZeoTech, Tucher (Bavaria) self-cooling beer barrel for 20/10 L of beer, first example on the German market

11 Example 2, Cold from low temperature heat New very compact systems of adsorption HP based on new zeolites AQSOA

12 Example 3, heating ZeoTHERM, since 4/2010 on the German market, Combination of gas burning/condensing application, adsorption heat pump and solar heat collector, energy savings up to 35%

13 Example 4 (Continuation) Integration of a adsorption heat pump (AHP) based on zeolites

14 Example 5 Storage for drying Dishwasher, A. Hauer, ZAE Bayern, Bosch/Siemens, 3 years on the German market, energy savings ca. 25% Charging during washing Zeolite Discharging for drying

15 Example 5 (continuation, A. Hauer) Energy Consumption: Conventional Dishwasher Dishwasher with TES Energy Saving (about 25 %) 1.05 kwh 0.80 kwh 0.25 kwh Conditions: Washing per year 250 Liftime 10 years Dishwasher produced per year 2,0 Mio. 1kWh = 0,5kg CO 2 (EU-Energymix) Energy Savings per year GWh Energy Savings after 10 years TWh CO 2 emission reduction 562,500 t

16 Modification of adsorption properties Introduction of zeotypes AlPO/SAPO into the energy transformation and storage technique, tailored shapes of water adsorption isotherms Berlin/Wildau Group, 9/2002 ISHPC Shanghai, AlPO-5, AlPO-18 Mitsubishi Chemical Group, 2/2002 FAM-Z01 and FAM-Z Almino-Silicate Zeolite Amount of Adsorbent [kg-h2/kg-adsorbent] FAM-Z02 FAM-Z01 Silica Gel Activated Carbon 0 Crystal of FAM(SEM photograph) Relative Pressure [-] We explored AlPOs and selected optimum structure and controlled surface hydrophobicity. We have succeeded in developing FAM-Z01 and FAM-Z02 for desired adsorbents. 30 micron

17 Results Univ. Erlangen/SorTech AG Halle (1) In-situ Coating of different support geometries with SAPO, AlPO for AHP (W. Schwieger, R. Herrmann, W. Mittelbach, J. Bauer) Variation of macro structure Variation of fluid dynamic properties High specific adsorbent loading Enhanced transport processes Low pressure drop High efficiency High specific power

18 EU-Project Technological development and demonstration of novel compact seasonal thermal energy systems 5 European countries (AT, CH, DK, GER, UK) 4 years period project, started in 2012 Main objective: Arrive at demonstrated systems for seasonal storage of solar thermal energy significantly better than water based systems for single family dwelling Parallel development of three technologies: A: Solid sorption, Water/new binderless Zeolite B: Liquid sorption, Water/NaOH C: Supercooling PCM,

19 Results CWK Bad Köstritz Binderless zeolite beads, development of new manufacturing technology and new factory (K. Schumann, A. Brandt, B. Unger, F. Scheffler) Binderless zeolite beads of type 13XBF 13X with binder

20 Conclusions -In recent years some new products appeared on the market with potential of mass production using thermal adsorption storage and heat transformation, - this results in growing interest of zeolite manufacturer in this field, - D&R for thermal applications focus on: # fine tuning of standard materials by chemical modifications, # specific synthesis of new materials, # in-situ coating of heat exchanger by direct synthesis, # materials for seasonal storage of solar heat. Significant contribution to energy savings and greener energy supply possible.

21 The financial support of parts of this work by the European Union s Seventh Framework Programme (FP7/ ), under grant agreement No , is acknowledged. Thank you for your attention!