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NL2035791B1 - a system comprising a form stable thermochemical material - Google Patents

a system comprising a form stable thermochemical material Download PDF

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Publication number
NL2035791B1
NL2035791B1 NL2035791A NL2035791A NL2035791B1 NL 2035791 B1 NL2035791 B1 NL 2035791B1 NL 2035791 A NL2035791 A NL 2035791A NL 2035791 A NL2035791 A NL 2035791A NL 2035791 B1 NL2035791 B1 NL 2035791B1
Authority
NL
Netherlands
Prior art keywords
thermochemical
particles
gas
permeable material
liquid
Prior art date
Application number
NL2035791A
Other languages
Dutch (nl)
Inventor
Maria Mazur Natalia
Aarts Joey
Clemens Gerardus Adan Olaf
Rudolph Fischer Hartmut
Original Assignee
Univ Eindhoven Tech
Tno
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Univ Eindhoven Tech, Tno filed Critical Univ Eindhoven Tech
Priority to NL2035791A priority Critical patent/NL2035791B1/en
Priority to PCT/NL2024/050497 priority patent/WO2025058515A1/en
Application granted granted Critical
Publication of NL2035791B1 publication Critical patent/NL2035791B1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00Products made by additive manufacturing
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28DHEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/003Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14Thermal energy storage

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Thermal Insulation (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Ceramic Products (AREA)

Abstract

The present invention relates to a system comprising a form stable thermochemical entity. The present invention also relates to a heat storage system and to the use of a system comprising a thermochemical entity. An object of the present invention is to provide a system comprising a thermochemical entity in which the thermochemical material shows a high cyclic form stability.

Description

Title: a system comprising a form stable thermochemical material
Description:
The present invention relates to a system comprising a thermochemical material (TCM). The present invention also relates to a heat storage system and to the use of a system comprising a thermochemical material (TCM).
International application WO 2019/038292 in the name of the present applicants discloses a closed-cycle thermal energy storage system comprising a thermochemical reactor containing a solid thermochemical material. In the TCM heat storage reaction, the TCM has two states, a salt complex, and a salt. The TCM charging involves the absorption of heat by the TCM and the release of sorbent gas.
The TCM discharging involves the release of heat by the TCM and the sorption of a working gas or liquid. The main criteria of success for such storage technique are highly efficient energy density, cost efficiency (short payback time), safety, and durability.
Thermochemical composites as such are known in the art. Methods aiming to create thermochemical entities through encapsulation are disclosed in, inter alia, B.
G. P. van Ravensteijn et al., “Encapsulation of Salt Hydrates by Polymer Coatings for
Low-Temperature Heat Storage Applications,” ACS Appl. Polym. Mater., vol. 3, no. 4, pp. 1712-1726, Apr. 2021, doi: 10.1021/acsapm.0c01186 and A. Shkatulov, R.
Joosten, H. Fischer, and H. Huinink, “Core-Shell Encapsulation of Salt Hydrates into
Mesoporous Silica Shells for Thermochemical Energy Storage,” ACS Appl. Energy
Mater., vol. 3, no. 7, pp. 6860-6869, Jul. 2020, doi: 10.1021/acsaem.0c00971.
However, these methods may generate some technical problems, for example aninconsistent and low power output, volume changes over cycles, disintegration, low energy density, difficult recyclability, and difficult preparation method.
Current thermochemical entities have shortcomings that hamper the introduction of their application in heat batteries and heat pumps, such as agglomeration and mechanical instabilities leading to cracking, dust formation and disintegration. There is thus a need for improved TCM-based heat storage systems.
An object of the present invention is to provide a system comprising a thermochemical material (TCM) in which the thermochemical material shows a high cyclic form stability.
An object of the present invention is to provide a system comprising a thermochemical material (TCM) that is easy to manufacture and to recycle.
An object of the present invention is to provide a heat storage system comprising a thermochemical material (TCM) in which the heat storage system shows a consistent and high power output over multiple (dis)charge cycles.
In addition, another object of the present invention is to provide a system comprising a thermochemical material (TCM) in which dust formation and disintegration of the TCM is reduced to a minimum.
The present invention as mentioned above is related to a system comprising a thermochemical material capable of storing and releasing heat by a thermochemical exchange process under release or binding of a gas or liquid, wherein the thermochemical material comprises particles, a plurality of particles being enclosed by a gas or liquid permeable material, the gas or liquid permeable material being impermeable for the thermochemical material.
On basis of the above the present inventors found a system that is suitable for heat storage and heat pump applications. The present invention consists of a thermochemical material (TCM) which is surrounded by a gas or liquid permeable shell. Due to the combination of thermochemical material properties and the shell properties, an entity with an exceedingly long cyclic lifetime is created, so it can be used in a heat battery or heat pump without the need of (early) replacement. The present inventors found that the present system comprising a thermochemical material has a high and constant power output over charging/discharging cycles, does not suffer from agglomeration or progressive swelling and is mechanically stable, without chemical material loss in time.
According to an example the particles are enclosed by the gas or liquid permeable material forming an enclosure. Such construction ensures that the thermochemical material is confined in an enclosure, i.e. due to the mechanical properties of the enclosure material, i.e. gas or liquid permeable but impermeable for the thermochemical material.
According to an example the particles in the enclosure are in a loose fit condition.
According to another example the particles in the enclosure are in a compacted condition.
According to an example the enclosure is provided with a mechanic support.
According to an example the system comprises a plurality of individual enclosures consisting of the permeable material, said enclosures being provided with the particles.
According to an example the individual enclosures are interconnected to form a construction consisting of a plurality of individual enclosures.
According to an example the permeable material is thermal stable in the temperature range where the thermochemical exchange process takes place.
According to an example the permeable material is chemical compatible with the thermochemical material.
According to an example the enclosure is not a coating. In addition, the particles are not provided with a coating of the gas or liquid permeable material.
The present invention also relates to a heat storage system comprising at least one system as discussed above.
An example of such a heat storage system is a heat battery based on thermochemical principles.
The present invention also relates to the use of a system as discussed above in beds in convective thermochemical reactors and in vacuum reactors for obtaining a stable reactor performance including power output with charging and discharging cycles.
The system as discussed above can be used in a chemical heat pump.
The present invention thus relates to a thermochemical entity based on a combination of a thermally stable and gas or liquid permeable material which contains a thermochemical material. The gas or liquid permeable material can be seen as a shell for the thermochemical material and must not be confused with the function of a coating.
The present system comprising a thermochemical material is suitable for application inside convective thermochemical reactors as well as vacuum reactors.
These can be a heat battery, heat pump or a combination of both systems. In a convective thermochemical reactor, the thermochemical entity results in a constant pressure drop in the reactor due to the shape stable nature of the entity. In a vacuum reactor the shape stable nature prevents creeping of the thermochemical material. The performance of such a thermochemical reactor and power output are therefore constant with consecutive (dis)charge cycles.
The shell in the present system comprising a thermochemical material capable of storing and releasing heat by a thermochemical exchange process under release or binding of a gas or liquid has such a vapor permeability that the performance of the thermochemical material is not hindered.
The shell may consist of a flexible material. The benefit of such a flexible material is that the shell adapts to a reorganization of the thermochemical material it contains. The material of the shell possesses a thermal stability in the charging temperature range of the thermochemical material and is also chemical compatible with the thermochemical material. Initial reorganization of the thermochemical material can exert an outward pressure on the flexible shell, resulting in mechanical stiffening of the whole entity.
Due to the nature of the shell material, different shapes of the entity are possible, such as particle like structures with varying curvatures, plate like structure, spheres, complex geometries, and combinations thereof. The stiffness of the entity can be changed by varying the content of thermochemical material and the nature of the shell material. The stiffness can range from very flexible to very stiff. Additional stiffness can be achieved through compacting of the thermochemical material inside the shell or the application of a built-in skeleton inside the shell, or a rearrangement of the thermochemical material inside the shell due to the thermochemical reaction.
The present inventors found that the thermochemical material does not show densification with consecutive (dis)charge cycles. The shell material prevents agglomeration of individual entities. The performance and (high) power output of the entity is stable for all (dis)charge cycles, resulting in stable material performance due to the shell. The entity remains mechanically intact with consecutive (dis)charge cycles. Moreover, the present inventors found that the thermochemical material is shape stable without dust formation or leakage.
The invention will be explained in more detail with the following figures and examples, without being restricted thereto.
A non-woven material (20-50 g/m?) is used as the gas or liquid permeable material and a bag thereof is manufactured by cutting material and sealing on three sides. The bag thus obtained is filled with TCM and afterwards sealed.
The bag was processed under the following conditions: dehydration 145 deg.
C. in vacuum oven under reduced pressure (3 mbar absolute pressure), hydration in 33% RH or 43% RH with exposure from 1 or 2 sides (desiccator). The average power at 50% conversion (per kg of anhydrous salt) was measured. The results are shown in 5 Table 1. The results of the thermochemical entity, i.e. the bag filled with TCM, is compared to a compacted TCM construction.
Table 1: Power output [Wikg] bag SE 35,201 hag esa #01 bg ri | 33,202
The conditions mentioned in Table 1 are: RH [%], T [deg. C.], # exposed sides [-].
The bag as manufactured above was subjected to a series of 30 (dis)charge cycles. The TCM material did not show any agglomeration, any swelling, maintained a mechanical stable condition and had a constant power output. Additional experiments were carried out for investigating the variation in thickness during cycles of dehydration and hydration. The experimental results thereof demonstrated form stability for 30 consecutive (dis)charge cycles, with an initial and minor increase in dimension in the first cycle only.
Figure 1 shows the inside of a system comprising a thermochemical material according to the present invention. Reference number 1 is a space to be filled with thermochemical material (not shown here). Reference number 3 is a gas or liquid permeable material. Reference number 2 is a mechanic support and forms the individual spaces for the thermochemical material. After filing the spaces 1 with thermochemical material the complete construction is covered with another layer of gas or liquid permeable material 3 and both layers of gas or liquid permeable material 3 are connected to each other thereby forming the system comprising a thermochemical entity.
Figure 2 shows an example of a system comprising a thermochemical material, in which the thermochemical material 5 is enclosed by two layers of gas or liquid permeable material 4.

Claims (14)

CONCLUSIESCONCLUSIONS 1. Systeem omvattende een thermochemisch materiaal dat in staat is om warmte op te slaan en vrij te geven door een thermochemisch uitwisselingsproces onder vrijgave of binding van een gas of vloeistof, waarbij het thermochemisch materiaal deeltjes omvat, waarbij een veelvoud van deeltjes is omsloten door een gas- of vloeistof doorlatend materiaal, waarbij het gas- of vloeistof doorlatende materiaal ondoordringbaar is voor het thermochemisch materiaal.1. A system comprising a thermochemical material capable of storing and releasing heat by a thermochemical exchange process while releasing or binding a gas or liquid, the thermochemical material comprising particles, a plurality of the particles being enclosed by a gas or liquid permeable material, the gas or liquid permeable material being impermeable to the thermochemical material. 2. Systeem volgens conclusie 1, waarbij de deeltjes zijn omsloten door het gas- of vloeistof doorlatende materiaal dat een omhulling vormt.2. A system according to claim 1, wherein the particles are enclosed by the gas- or liquid-permeable material forming an envelope. 3. Systeem volgens een of meer van de voorgaande conclusies, waarbij de deeltjes in de omhulling zich in een losse pasvorm bevinden.3. A system according to any preceding claim, wherein the particles in the enclosure are in a loose fit. 4. Systeem volgens een of meer van de conclusies 1-2, waarbij de deeltjes in de omhulling zich in een gecompacteerde toestand bevinden.4. A system according to any one of claims 1 to 2, wherein the particles in the envelope are in a compacted state. 5. Systeem volgens een of meer van de conclusies 1-4, waarbij de omhulling is voorzien van een mechanische ondersteuning.5. System according to one or more of claims 1 to 4, wherein the enclosure is provided with a mechanical support. 6. Systeem volgens een of meer van de conclusies 2-5, waarbij het systeem meerdere individuele omhulsels omvat bestaande uit het doorlaatbare materiaal, waarbij de omhullingen zijn voorzien van de deeltjes.6. A system according to any one of claims 2 to 5, wherein the system comprises a plurality of individual shells comprising the permeable material, the shells being provided with the particles. 7. Systeem volgens conclusie 6, waarbij de individuele omhullingen met elkaar zijn verbonden tot een constructie bestaande uit meerdere individuele omhullingen.7. System according to claim 6, wherein the individual enclosures are connected to each other to form a structure consisting of a plurality of individual enclosures. 8. Systeem volgens een of meer van de voorgaande conclusies, waarbij het doorlaatbare materiaal thermisch stabiel is in het temperatuurbereik waarin het thermochemische uitwisselingsproces plaatsvindt.8. A system according to any preceding claim, wherein the permeable material is thermally stable in the temperature range in which the thermochemical exchange process takes place. 9. Systeem volgens een of meer van de voorgaande conclusies, waarbij het doorlaatbare materiaal chemisch compatibel is met het thermochemisch materiaal.9. A system according to any preceding claim, wherein the permeable material is chemically compatible with the thermochemical material. 10. Systeem volgens een of meer van de voorgaande conclusies, waarbij de deeltjes niet zijn voorzien van een coating van het gas- of vloeistof doorlatende materiaal.10. A system according to any one or more of the preceding claims, wherein the particles are not provided with a coating of the gas- or liquid-permeable material. 11. Warmteopslagsysteem omvattende ten minste een systeem volgens een of meer van de voorgaande conclusies.11. Heat storage system comprising at least one system according to one or more of the preceding claims. 12. Warmteopslagsysteem volgens conclusie 11, waarbij het warmteopslagsysteem een op thermochemische principes gebaseerde warmtebatterij is.12. Heat storage system according to claim 11, wherein the heat storage system is a heat battery based on thermochemical principles. 13. Toepassing van een systeem volgens een of meer van de conclusies 1-10 in bedden in convectieve thermochemische reactoren en in vacuümreactoren voor het verkrijgen van stabiele reactorprestaties, inclusief vermogensafgifte met laad- en ontlaadcycli.13. Use of a system according to any one of claims 1 to 10 in beds in convective thermochemical reactors and in vacuum reactors for obtaining stable reactor performance, including power output with charge and discharge cycles. 14. Toepassing van een systeem volgens een of meer van de conclusies 1-10 in een chemische warmtepomp.14. Use of a system according to one or more of claims 1 to 10 in a chemical heat pump.
NL2035791A 2023-09-13 2023-09-13 a system comprising a form stable thermochemical material NL2035791B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
NL2035791A NL2035791B1 (en) 2023-09-13 2023-09-13 a system comprising a form stable thermochemical material
PCT/NL2024/050497 WO2025058515A1 (en) 2023-09-13 2024-09-12 A system comprising a form stable thermochemical material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL2035791A NL2035791B1 (en) 2023-09-13 2023-09-13 a system comprising a form stable thermochemical material

Publications (1)

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NL2035791B1 true NL2035791B1 (en) 2025-03-21

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WO (1) WO2025058515A1 (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5626936A (en) 1993-09-09 1997-05-06 Energy Pillow, Inc. Phase change insulation system
DE102006010636A1 (en) * 2005-12-19 2007-06-21 BLüCHER GMBH Sorption storage unit for gases
GB2495938A (en) 2011-10-25 2013-05-01 Univ Nottingham Energy storage apparatus
WO2014104886A1 (en) 2012-12-27 2014-07-03 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Composite material for heat storage, method for preparation and use
WO2019038292A1 (en) 2017-08-22 2019-02-28 Technische Universiteit Eindhoven Closed cycle thermal energy storage system using thermochemical material
DE102019205788A1 (en) 2019-04-23 2020-10-29 Deutsches Zentrum für Luft- und Raumfahrt e.V. Thermal storage device and method for manufacturing a storage unit
WO2022231422A1 (en) * 2021-04-26 2022-11-03 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Compacted thermochemical heat storage bodies
WO2023053859A1 (en) 2021-09-30 2023-04-06 キヤノンオプトロン株式会社 Heat storage structure and heat storage system

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